CN114200039A - Method for detecting HF content in fluorine gas - Google Patents
Method for detecting HF content in fluorine gas Download PDFInfo
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- CN114200039A CN114200039A CN202111410785.6A CN202111410785A CN114200039A CN 114200039 A CN114200039 A CN 114200039A CN 202111410785 A CN202111410785 A CN 202111410785A CN 114200039 A CN114200039 A CN 114200039A
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 104
- 239000011737 fluorine Substances 0.000 title claims abstract description 104
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims description 133
- 238000005070 sampling Methods 0.000 claims description 53
- 238000010521 absorption reaction Methods 0.000 claims description 46
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Substances [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- 239000001103 potassium chloride Substances 0.000 claims description 6
- 235000011164 potassium chloride Nutrition 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical group [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 229910001513 alkali metal bromide Inorganic materials 0.000 claims description 5
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims description 5
- 229910001516 alkali metal iodide Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052704 radon Inorganic materials 0.000 claims description 3
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 3
- 235000009518 sodium iodide Nutrition 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910001209 Low-carbon steel Inorganic materials 0.000 claims description 2
- 229910000792 Monel Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000856 hastalloy Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 238000001514 detection method Methods 0.000 abstract description 18
- 239000012535 impurity Substances 0.000 abstract description 8
- 239000007788 liquid Substances 0.000 description 19
- 239000003513 alkali Substances 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 238000010926 purge Methods 0.000 description 13
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 12
- 239000012498 ultrapure water Substances 0.000 description 9
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- -1 fluorine ions Chemical class 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 7
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 229910018503 SF6 Inorganic materials 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 3
- HXELGNKCCDGMMN-UHFFFAOYSA-N [F].[Cl] Chemical compound [F].[Cl] HXELGNKCCDGMMN-UHFFFAOYSA-N 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 229960000909 sulfur hexafluoride Drugs 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101100313175 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) TCD1 gene Proteins 0.000 description 1
- 101100313176 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) TCD2 gene Proteins 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/96—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 using ion-exchange
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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)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention discloses a method for detecting the content of HF (fluorine gas) in fluorine gas, which comprises the steps of removing the fluorine gas from a fluorine gas sample to be detected containing the HF through a fluorine gas conversion agent, and detecting the content of the HF in residual gas. The method of the invention overcomes the difficulty that HF gas can not be directly detected in the prior art, so that the detection of HF impurities in fluorine gas is more direct, convenient and accurate.
Description
Technical Field
The invention relates to the field of analytical chemistry, in particular to a method for detecting the content of HF in fluorine gas.
Background
Fluorine is a non-metallic element with the strongest electronegativity and the most active chemical property, and can react with almost all elements. Fluorine gas (F)2) Because of their reactive properties, they are used in the semiconductor industry as etching gases or cleaning gases for the production of photovoltaic cells and TFTs (thin film transistors) for liquid crystal displays. F2As cleaning agent for CVD reaction chamber, with NF3Compared with the prior art, the preparation method has stronger reactivity and does not cause greenhouse effect; metal fluorides generated by the reaction of fluorine gas and metal tungsten or germanium, and the like, which can be used as vapor deposition gases or doping gases in the field of semiconductor manufacturing; the high-purity fluorine gas can be mixed with inert gases such as nitrogen, helium, neon, argon and the like in any concentration ratio to prepare mixed gas which is used as laser gas. Therefore, in the field of semiconductors, fluorine gas has great application potential, but the requirement of the industry on the purity of the fluorine gas is higher and higher, and the purity of the fluorine gas is gradually increased from 99.7 percent (volume ratio) to more than 99.99 percent (volume ratio). However, the analysis of each impurity in fluorine gas is difficult, particularly the analysis of HF, and no suitable analysis method is available in the industry.
The detection method specified in the national standard of the mixed gas of fluorine and nitrogen (GB/T2651-2010) is that fluorine gas to be detected firstly passes through a sodium fluoride adsorption column to remove entrained HF, then passes through a potassium chloride or sodium chloride adsorption column to convert the fluorine gas into chlorine gas, then the combined gas enters a fluorine-chlorine oil column to separate the chlorine gas, and a TCD1 detector is used for determining the content of the chlorine gas to replace the content of the fluorine gas. After the gas flows out of the fluorine-chlorine oil column, the gas firstly enters a metal column (Ag) to remove excessive fluorine gas and chlorine gas, then enters an aluminum oxide adsorption column and a molecular sieve column which are connected in series to remove excessive HF, fluorine gas and chlorine gas, and then enters a TCD2 detector to measure the content of impurities such as oxygen, nitrogen, carbon tetrafluoride and the like in the fluorine gas. As for the content of HF, it cannot be directly detected and is calculated by an exclusion method. Assuming that the total amount of fluorine gas and impurities to be detected is 100, the detection values of the impurities such as fluorine gas, oxygen gas, nitrogen gas, carbon tetrafluoride and the like are subtracted from the total amount of fluorine gas and impurities to be detected, and the remaining part is the content of HF. The accuracy of the data is relatively coarse and cannot reflect the true value.
The chinese patent CN 20705138U discloses a fluorine gas concentration analyzer, which can detect the concentration of fluorine gas conveniently, quickly and cheaply by chemical analysis. The specific method comprises the following steps: the fluorine gas to be detected is firstly purified by a purifying pipe to remove HF, and then is converted into chlorine gas in equal proportion by a conversion pipe. The purification tube is filled with alkali metal fluoride such as sodium fluoride and the like which can absorb HF gas; the conversion tube is filled with alkali chlorides such as potassium chloride and sodium chloride, and can react with fluorine gas to convert the fluorine gas into chlorine gas in equal proportion. Then the mixed gas converted into chlorine gas enters a quantitative pipe capable of accurately measuring the volume of the gas, the gas collected by the quantitative pipe is mixed with alkali solution by operating the quantitative pipe, the chlorine gas reacts with the alkali solution and is dissolved in the alkali solution, and the volume of the gas in the quantitative pipe is reduced. The reduced volume of the gas is equal to the content of fluorine gas in the mixed gas, and the residual amount is the content of impurity gases such as nitrogen, oxygen, carbon tetrafluoride and the like. In this way, the purity of the fluorine gas can be calculated, but the HF entrained in the fluorine gas is not in the detection range.
Due to the special physicochemical characteristics of HF gas, common fluorine gas detection methods cannot directly measure HF gas, and HF gas is removed by using fluoride salts such as sodium fluoride in the first step and then is subjected to subsequent treatment or detection. This results in complicated operation steps and inaccurate results. It is therefore desirable to find a method for direct detection of HF to solve the above problems.
Disclosure of Invention
One aspect of the invention provides a method for detecting the content of HF in fluorine gas, aiming at the defects of complex operation and low accuracy of the method for indirectly detecting the content of HF in fluorine gas in the prior art.
The technical scheme provided by the invention is as follows:
a method for detecting the content of HF in fluorine gas comprises the steps of removing the fluorine gas by passing a fluorine gas sample to be detected containing the HF through a fluorine gas conversion agent, and detecting the content of the HF in residual gas.
Specifically, in one embodiment of the present invention, the inventors achieve the object of the present invention by using the following technical solutions: firstly, a certain volume of fluorine gas to be detected is collected by using a constant volume sampling tube, then the fluorine gas is driven and replaced by high-purity nitrogen or inert gases such as helium, argon, radon and the like to enter a conversion column, and a fluorine gas conversion agent is filled in the conversion column, so that the fluorine gas can be converted into a substance which does not interfere with HF detection. Absorbing the converted mixed gas by using high-purity water or alkali liquor, and then measuring the concentration of fluorine ions in the high-purity water or alkali liquor by using an ion chromatograph or a selective fluorine ion electrode, wherein all the fluorine ions are converted from HF gas, and further calculating the HF content in the sampling tube.
In the present invention, the fluorine gas to be measured may be collected by any suitable method or apparatus. Preferably, in an embodiment of the present invention, the fluorine gas sample to be measured is collected and measured for volume by a constant volume sampling tube, and the constant volume sampling tube is made of a metal or an alloy. Preferably, in an embodiment of the present invention, the material of the constant volume sampling tube is one or more selected from nickel, monel, hastelloy, stainless steel, copper, and mild steel.
Furthermore, any suitable additional device can be arranged on the constant volume sampling tube to realize the corresponding function. Preferably, in an embodiment of the present invention, the volumetric sampling tube is further provided with a pressure sensor and/or a temperature sensor. The purpose of the use of the pressure sensor and/or the temperature sensor is to monitor that the temperature and the pressure of the sampling tube are kept stable after the sampling is finished.
One or more constant-volume sampling pipes can be arranged according to the volume of the fluorine gas to be detected, and are connected with the purging or replacement gas inlet.
In the present invention, the above method uses an inert gas to drive or replace the gas in the apparatus used. The driving function can be to drive the sample to be detected or other gases in the device into the corresponding device, and the displacement function can be to displace other gases in the device before the sample to be detected is introduced.
Preferably, in an embodiment of the present invention, the inert gas is one or more selected from nitrogen, helium, argon, and radon.
In the present invention, the fluorine gas converting agent described above may be stored in a specific container such as a conversion column. The fluorine gas converting agent is used for removing fluorine gas and reducing the influence on HF analysis in subsequent detection. The selection criteria are materials that react only with fluorine gas but not with HF.
The above-mentioned reforming column may be provided in one or more number depending on the volume of the fluorine gas to be detected. The above-mentioned conversion column may be added with a device having a corresponding function according to the requirements of the conversion reaction, for example, a heating device as shown in fig. 2.
Preferably, in an embodiment of the present invention, the fluorine gas converting agent is one or more selected from activated carbon, sulfur, alkali metal chloride, alkali metal bromide, and alkali metal iodide.
More preferably, in one embodiment of the present invention, the alkali metal chloride is sodium chloride and/or potassium chloride, the alkali metal bromide is sodium bromide and/or potassium bromide, and the alkali metal iodide is sodium iodide and/or potassium iodide.
The fluorine gas converting agent can convert fluorine gas into a substance which does not interfere with HF detection, and an HF analysis process needs to be adjusted according to the characteristics of different compounds, so that the aim of accurate analysis is fulfilled.
When the fluorine gas converting agent is activated carbon, the fluorine gas can be directly converted into carbon tetrafluoride, the carbon tetrafluoride is insoluble in water and alkali liquor, the converted gas can be absorbed by high-purity water or liquid alkali, and the fluorine ion content in the absorption liquid is analyzed and further converted into the content of HF in the fluorine gas. Because the reaction of fluorine and carbon needs to be heated, the temperature of the conversion column should be controlled between 200 ℃ and 250 ℃.
The reaction formula is as follows: 2F2+C→CF4
When the fluorine gas converting agent is sulfur, the fluorine gas can be directly converted into sulfur hexafluoride, the sulfur hexafluoride is insoluble in water and alkali liquor, the converted gas can be absorbed by high-purity water or liquid alkali, and the fluorine ion content in the absorption liquid is analyzed and further converted into the content of HF in the fluorine gas.
The reaction formula is as follows: 3F2+S→SF6
When the fluorine gas converting agent is alkali metal chloride such as potassium chloride, sodium chloride and the like, converting the fluorine gas into chlorine gas; absorbing the converted gas by using high-purity water or liquid caustic soda, analyzing the fluorine ion content in the absorption liquid, and converting the fluorine ion content into the content of HF in the fluorine gas.
The reaction formula is as follows: f2+2NaCL→2NaF+Cl2
F2+2KCL→2KF+Cl2
When the fluorine gas converting agent is an alkali metal bromide such as potassium bromide or sodium bromide, the fluorine gas is converted into bromine gas. The bromine gas has low solubility in water, and can be firstly absorbed by high-purity water, then absorbed by liquid alkali to absorb HF and bromine gas, and then the fluorine ion content in the absorption liquid is analyzed, so that the fluorine ion content is converted into the content of HF in fluorine gas.
The reaction formula is as follows: f2+2NaBr→2NaF+Br2
F2+2KBr→2KF+Br2
When the fluorine gas converting agent is an alkali metal iodide such as potassium iodide or sodium iodide, the fluorine gas can be directly converted into iodine. Iodine has low solubility in water, is solid at normal temperature and is easy to sublimate. A normal temperature buffer tank can be arranged behind the conversion column to collect iodine solid, the converted gas is absorbed by high-purity water or liquid caustic soda, and the fluorine ion content in the absorption liquid is analyzed, so that the fluorine ion content is converted into the content of HF in the fluorine gas.
The reaction formula is as follows: f2+2NaI→2NaF+I2
F2+2KI→2KF+I2
In the present invention, the detection of HF in the sample from which fluorine gas has been removed can be performed by any suitable method known in the art. Such as fourier spectrophotometers and gas chromatography, among others. However, in an embodiment of the present invention, the detection of the HF content in the residual gas is preferably performed by detecting the fluoride ion concentration after absorbing HF in the residual gas.
The absorption can be carried out in an absorption device, for example, an absorption bottle. In order to ensure the sufficient and complete HF absorption, a plurality of absorption bottles containing the absorption liquid can be used in series, and the specific number of the absorption bottles is determined by the sampling amount of the fluorine gas.
Preferably, in one embodiment of the present invention, the absorption is performed by using high purity water or alkali solution to absorb the HF. Before detection, high-purity water and alkali liquor must be quantified, and new absorption liquid must be used for each analysis.
In the present invention, any suitable method or apparatus may be used for detecting the fluoride ion concentration. Preferably, however, the fluorine ion concentration is detected by using an ion chromatograph or a selective fluorine ion electrode when the volume percentage of HF in the residual gas is less than 3%.
Since ion chromatography or selective fluoride ion electrodes are not suitable for the detection of high concentrations of HF. However, after fluorine gas prepared by the electrolysis method is removed at low temperature and is adsorbed by alkali metal fluorides such as sodium fluoride and the like, the HF content is reduced to be below 3.0 percent (volume ratio), and after the absorption liquid is absorbed, an ion chromatograph or a selective fluorine ion electrode can be used for accurately measuring the fluorine ion concentration so as to convert the fluorine ion concentration into the HF content.
According to the analysis method provided by the implementation of the invention, as shown in fig. 1, the process route comprises a fluorine gas sampling valve 1, an inert gas purging valve 2, a constant volume sampling pipe 3, a temperature detection 4, a pressure detection 5, a conversion column inlet valve 6, a conversion column 7, a conversion column outlet valve 8, a secondary conversion column inlet valve 9, a secondary conversion column 10, a secondary conversion column outlet valve 11, a vacuum pumping valve 12, an absorption bottle inlet valve 13, a 1# absorption bottle 14, a 2# absorption bottle 15, a 3# absorption bottle 16, an absorption bottle outlet valve 17 and a vacuum pump 18.
The sampling method for realizing the invention comprises the following steps:
firstly, detecting the sealing performance of a conversion column and an absorption bottle, opening a purge valve 2, filling nitrogen into a sampling pipe 3 at the pressure of less than or equal to 0.1MPa, and gradually opening a valve 6, a valve 8, a valve 9, a valve 11 and a valve 13. The whole analysis sampling pipeline is filled with inert gas for positive pressure leakage test, and the next step can be carried out without leakage.
And secondly, vacuumizing, wherein the whole analysis process pipeline is evacuated before sampling, the sampling valve 1, the purge valve 2, the absorption bottle inlet valve 13 and the absorption bottle outlet valve 17 are closed, the valve 6, the valve 8, the valve 9, the valve 11 and the vacuumizing valve 12 are sequentially opened, the vacuum pump 18 is started, the vacuum is vacuumized for more than 20min, and the vacuum degree of the constant volume sampling tube 3 is less than or equal to 0.09 MPa.
And thirdly, sampling, closing the valve 6, the valve 2 and the valve 12, opening the sampling valve 1, filling fluorine gas into the sampling pipe 3, and closing the sampling valve 1 after the pressure is stable and is less than or equal to 0.1 MPa. The pressure P (MPa) and temperature t (deg.C) of the sampling tube are registered at this time. On the basis of which the amount of gas in the sampling tube can be calculated.
And fourthly, fluorine gas is converted, a valve 6 is opened, and the fluorine gas in the sampling pipe 3 enters a conversion column 7 and a secondary conversion column 10 to be converted into other substances.
And fifthly, purging and replacing, namely opening the purging valve 2, the inlet valve 13 of the absorption bottle and the outlet valve 17 of the absorption bottle, and enabling the inert purging gas to enter the analysis sampling process pipeline. Starting the vacuum pump 18, purging and replacing for more than 30 min.
And sixthly, closing the valve 13 and the valve 17 after sampling is finished, opening the valve 12, and closing each valve and stopping the operation of the vacuum pump 18 or performing secondary sampling after the analysis sampling process continues to purge, replace and evacuate for more than 20 min.
Seventhly, analyzing the concentration of the fluorine ions, and removing the absorption bottle 1#、2#、3#Analyzing the fluorine ion concentration in the absorption liquid by using an ion chromatograph or a selective fluorine ion electrode, wherein n is respectively1、n2、n3(mol/L). Assuming that the volume of the absorption liquid in each absorption bottle is V1、V2、V3(L), then, the HF content is converted to n (HF).
n(HF)＝n1V1+n2V2+n3V3
The eighth step, the content of HF in the fluorine gas is calculated, then
The invention has the beneficial effects that:
the method of the invention overcomes the difficulty that HF gas can not be directly detected in the prior art, so that the detection of HF impurities in fluorine gas is more direct, convenient and accurate.
Drawings
FIG. 1 is a process flow diagram of a detection method in an embodiment of the invention;
FIG. 2 is a structural diagram of a reforming column with a heating temperature control device in an embodiment of the present invention.
Detailed Description
The invention discloses a method for detecting the content of HF in fluorine gas, and a person skilled in the art can appropriately improve process parameters by referring to the content. It is expressly intended that all such alterations and modifications which are obvious to those skilled in the art are deemed to be incorporated herein by reference, and that the techniques of the invention may be practiced and applied by those skilled in the art without departing from the spirit, scope and range of equivalents of the invention.
In the present invention, unless otherwise specified, scientific and technical terms used herein have the meanings that are commonly understood by those skilled in the art. Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component. The terms "such as," "e.g.," and the like are intended to refer to exemplary embodiments and are not intended to limit the scope of the present disclosure.
In order to make those skilled in the art better understand the technical solution of the present invention, the following detailed description of the present invention is provided with reference to specific embodiments.
Example 1:
the volume of the constant volume sampling tube 3 is 3L, the conversion column 7 and the secondary conversion column 10 are heated and controlled in temperature, the temperature is controlled between 200 and 300 ℃, and the conversion column is filled with active carbon. The absorption solution uses 5% sodium hydroxide solution, the absorption bottles are 4 in total, the first 3 absorption bottles are each filled with 0.5L absorption solution, the 4 th bottle is empty, and the operation is strictly carried out according to the sampling steps. And after the fluorine gas sample introduction is finished, closing the sampling valve, and setting the temperature of the sampling pipe 3 to be 21 ℃ and the pressure to be 0.097 MPa.
The total sampling amount is:
purging with nitrogen, replacing, evacuating for 30min, and analyzing with ion chromatograph to obtain fluoride ion concentrations n1＝360.0×10-6(mol/L)；n2＝58.0×10-6(mol/L)；n3＝0.92×10-6(mol/L). The total amount of fluorine ions is
n(HF)＝(360×10-6+58×10-6+0.92×10-6)×0.5＝209.46×10-6(mol)
The content of HF in the fluorine gas is as follows according to the data:
example 2:
the volume of the constant volume sampling tube 3 is 3L, the conversion column 7 and the second-stage conversion column 10 use normal temperature columns, and sulfur is filled in the conversion column. The absorption solution uses 5% sodium hydroxide solution, the absorption bottles are 4 in total, the first 3 absorption bottles are each filled with 0.5L absorption solution, the 4 th bottle is empty, and the operation is strictly carried out according to the sampling steps. And after the fluorine gas sample introduction is finished, closing the sampling valve, and setting the temperature of the sampling pipe 3 to be 21 ℃ and the pressure to be 0.091 MPa.
The total sampling amount is:
purging with nitrogen, displacing, evacuating for 30min, and analyzing with fluorine ion selective electrode to obtain fluorine ion concentrations n1＝182.0×10-6(mol/L)；n2＝38.0×10-6(mol/L)；n3＝0.3×10-6(mol/L). The total amount of fluorine ions is
n(HF)＝(182.0×10-6+38.0×10-6+0.3×10-6)×0.5＝110.15×10-6(mol)
The content of HF in the fluorine gas is as follows according to the data:
example 3:
the volume of the constant volume sampling tube 3 is 3L, the conversion column 7 and the second-stage conversion column 10 use normal temperature columns, and the conversion column is filled with potassium chloride. The absorption liquid uses 5% sodium hydroxide solution, 4 absorption bottles in total, 1 liter of absorption liquid is filled into each of the first 3 absorption bottles, and the 4 th bottle is an empty bottle, and the operation is strictly carried out according to the sampling step. And after the fluorine gas sample introduction is finished, closing the sampling valve, and setting the temperature of the sampling tube 3 to be 21 ℃ and the pressure to be 0.085 MPa.
The total sampling amount is:
purging with nitrogen, replacing, evacuating for 30min, and analyzing with ion chromatograph to obtain fluoride ion concentrations n1＝97.0×10-6(mol/L)；n2＝11.0×10-6(mol/L)；n30.1X 10-6 (mol/L). The total amount of fluorine ions is
n(HF)＝(97.0×10-6+11.0×10-6+0.1×10-6)×1.0＝108.1×10-6(mol)
The content of HF in the fluorine gas is as follows according to the data:
example 4:
the volume of the constant volume sampling tube 3 is 3L, the conversion column 7 and the second-stage conversion column 10 use normal temperature columns, and the conversion column is filled with potassium iodide. The absorption liquid uses 5% sodium hydroxide solution of concentration, and the absorption bottle is 5 in total, and the first is empty bottle, is used for collecting the iodine solid, and 2 nd, 3 rd, 4 th absorption bottled alkali lye, 1 liter of absorption liquid is packed into to each, and the 5 th is empty bottle and connects vacuum pump 18, strictly operates according to the sampling step. And after the fluorine gas sample introduction is finished, closing the sampling valve, and setting the temperature of the sampling pipe 3 to be 21 ℃ and the pressure to be 0.095 MPa.
The total sampling amount is:
purging with nitrogen, replacing, evacuating for 30min, and analyzing with ion chromatograph to obtain fluoride ion concentrations n1＝63.0×10-6(mol/L)；n2＝7.0×10-6(mol/L)；n3＝0.01×10-6(mol/L). The total amount of fluorine ions is
n(HF)＝(63.0×10-6+7.0×10-6+0.01×10-6)×1.0＝108.1×10-6(mol)
The content of HF in the fluorine gas is as follows according to the data:
the foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for detecting the content of HF in fluorine gas is characterized in that a fluorine gas sample to be detected containing HF is passed through a fluorine gas conversion agent to remove the fluorine gas, and the content of HF in the residual gas is detected.
2. The method as claimed in claim 1, wherein the fluorine gas sample to be measured is collected and measured for volume through a constant volume sampling tube, and the constant volume sampling tube is made of metal or alloy, preferably one or more selected from nickel, Monel, Hastelloy, stainless steel, copper or low carbon steel.
3. The method according to claim 2, wherein the volumetric sampling tube is further provided with a pressure sensor and/or a temperature sensor.
4. A method according to claim 1, characterized in that the gas in the apparatus used is driven off or replaced by an inert gas.
5. The method according to claim 1, wherein the inert gas is one or more selected from nitrogen, helium, argon or radon.
6. The method of claim 1, wherein the fluorine gas converting agent is one or more selected from activated carbon, sulfur, alkali metal chloride, alkali metal bromide, or alkali metal iodide.
7. The method of claim 6, wherein the alkali metal chloride is sodium chloride and/or potassium chloride, the alkali metal bromide is sodium bromide and/or potassium bromide, and the alkali metal iodide is sodium iodide and/or potassium iodide.
8. The method according to claim 1, wherein said detecting the HF content of the residual gas is performed by detecting the fluoride ion concentration after absorbing HF in the residual gas.
9. The method according to claim 8, wherein the absorption is of the HF using highly pure water or lye.
10. The method of claim 8, wherein the residual gas has a percentage of HF by volume of less than 3% and the detecting the fluoride ion concentration is performed using an ion chromatograph or a selective fluoride ion electrode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114814039A (en) * | 2022-05-24 | 2022-07-29 | 福建德尔科技股份有限公司 | Method for analyzing content of impurities in fluorine gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472146A (en) * | 2013-08-19 | 2013-12-25 | 广东电网公司电力科学研究院 | Method for measuring content of chloridion and fluorinion in solid biomass fuel |
| CN107290437A (en) * | 2016-03-31 | 2017-10-24 | 中核新能核工业工程有限责任公司 | The method for measuring content of fluorine indirectly using chromatograph |
| CN207832754U (en) * | 2017-12-13 | 2018-09-07 | 山东非金属材料研究所 | A kind of chlorine ionization reforming unit |
| 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 |
-
2021
- 2021-11-25 CN CN202111410785.6A patent/CN114200039A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103472146A (en) * | 2013-08-19 | 2013-12-25 | 广东电网公司电力科学研究院 | Method for measuring content of chloridion and fluorinion in solid biomass fuel |
| CN107290437A (en) * | 2016-03-31 | 2017-10-24 | 中核新能核工业工程有限责任公司 | The method for measuring content of fluorine indirectly using chromatograph |
| CN207832754U (en) * | 2017-12-13 | 2018-09-07 | 山东非金属材料研究所 | A kind of chlorine ionization reforming unit |
| 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 |
Non-Patent Citations (5)
| Title |
|---|
| 方华;庄鸿涛;杨康;: "GC9560-HF气相色谱仪在氟气纯度分析中的应用", 低温与特气, no. 06, 15 December 2009 (2009-12-15) * |
| 曹晴;张艳平;谭玉玲;刘宇;王洪昌;王相凤;张凡;: "离子色谱法测定烟气中的氟和氯", 环境工程技术学报, no. 02, 20 March 2017 (2017-03-20) * |
| 杜卫莉;: "离子色谱测定磷肥生产过程中大气污染物中的氟化氢", 广州化工, no. 02, 15 April 2009 (2009-04-15), pages 1 * |
| 杨一超, 赵丽生: "离子色谱法同时测定工作场所空气中HF、HCl、H_2SO_4", 中国卫生检验杂志, no. 04, 25 August 2005 (2005-08-25) * |
| 赵智霞;曾昌华;朱成财;张勇;: "环境中微量氟化氢的含量监测", 有机氟工业, no. 04, 30 December 2006 (2006-12-30) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114814039A (en) * | 2022-05-24 | 2022-07-29 | 福建德尔科技股份有限公司 | Method for analyzing content of impurities in fluorine gas |
| CN114814039B (en) * | 2022-05-24 | 2022-11-11 | 福建德尔科技股份有限公司 | Method for analyzing content of impurities in fluorine gas |
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