CN117358170A - Device and method for preparing high-purity fluorine gas - Google Patents
Device and method for preparing high-purity fluorine gas Download PDFInfo
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- CN117358170A CN117358170A CN202311134530.0A CN202311134530A CN117358170A CN 117358170 A CN117358170 A CN 117358170A CN 202311134530 A CN202311134530 A CN 202311134530A CN 117358170 A CN117358170 A CN 117358170A
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 106
- 239000011737 fluorine Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000012798 spherical particle Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000010926 purge Methods 0.000 claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical class F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 15
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- YPDSOAPSWYHANB-UHFFFAOYSA-N [N].[F] Chemical compound [N].[F] YPDSOAPSWYHANB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910000792 Monel Inorganic materials 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- FWZMWMSAGOVWEZ-UHFFFAOYSA-N potassium;hydrofluoride Chemical compound F.[K] FWZMWMSAGOVWEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 4
- 239000010962 carbon steel Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- GOVXUOILKBXQJW-UHFFFAOYSA-M fluoronickel Chemical class [Ni]F GOVXUOILKBXQJW-UHFFFAOYSA-M 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000005453 pelletization Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 116
- 238000000746 purification Methods 0.000 abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- -1 potassium fluoride hydride Chemical compound 0.000 abstract 1
- HHPKUIWWHLVHQQ-UHFFFAOYSA-L difluoronickel;tetrahydrate Chemical compound O.O.O.O.F[Ni]F HHPKUIWWHLVHQQ-UHFFFAOYSA-L 0.000 description 13
- VBKNTGMWIPUCRF-UHFFFAOYSA-M potassium;fluoride;hydrofluoride Chemical compound F.[F-].[K+] VBKNTGMWIPUCRF-UHFFFAOYSA-M 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 7
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000003825 pressing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- POHFBTRVASILTB-UHFFFAOYSA-M potassium;fluoride;dihydrofluoride Chemical compound F.F.[F-].[K+] POHFBTRVASILTB-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000011172 small scale experimental method Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/19—Fluorine; Hydrogen fluoride
- C01B7/20—Fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
Abstract
The application discloses a device for preparing high-purity fluorine gas, which comprises a reactor, a thermometer, a pressure gauge and N 2 Purging pipeline F 2 Air inlet pipeline F 2 An air outlet pipeline and a vacuumizing pipeline; the application also discloses a method for preparing the high-purity fluorine gas, which comprises the following steps: s1: adding nickel fluoride salt and potassium fluoride hydride according to a mole ratio into a stirrer, heating and stirring to form a mixture, and adding the mixture into a granulator to prepare spherical particles. S2: and (3) putting the spherical particles in the step (S1) into a reactor, reacting with nitrogen and fluorine mixed gas with the fluorine gas volume content of 20%, forming porous particles, and vacuumizing for later use. S3: introducing fluorine gas into the reactor, and controlling the reaction conditions to obtain K 3 NiF 7 And then vacuumizing for standby. S4: raising the temperature of the reactor to K 3 NiF 7 Decomposing to obtain high-purity fluorine gas. The method solves the production technical hidden trouble of fluorine gas purification in the prior art, and has the advantages of costThe cost is low, and the purity of the fluorine gas can be controlled to be more than 99.9 percent.
Description
Technical Field
The application belongs to the technical field of fluorine gas preparation, and particularly relates to a device and a method for preparing high-purity fluorine gas.
Background
Fluorine gas (F) 2 ) Is a very reactive gas with strong oxidizing properties and is used in the semiconductor industry as an etching gas or cleaning gas for the manufacture of photovoltaic cells and TFTs (thin film transistors) for liquid crystal displays due to its reactive nature. Meanwhile, as a gas of an excimer laser, a fluorine laser is also widely used in the semiconductor industry. At the same time utilize F 2 Cleaning agent used as Chemical Vapor Deposition (CVD) reaction chamber and NF 3 In comparison, F 2 Has stronger reactivity and does not cause greenhouse effect. Fluorine gas used for this purpose is greatly increasing in demand along with the vigorous development of the domestic semiconductor industry.
Industrially, the method for preparing fluorine gas by electrolysis comprises the following steps: and (3) electrolyzing KF.2HF (mixture of potassium hydroxide and hydrogen fluoride), taking compacted graphite as an anode, taking a steel electrolytic tank body as a cathode (or adopting a carbon plate or a nickel plate as the anode and adopting carbon steel as the cathode), taking potassium hydrogen fluoride as an electrolyte, carrying out electrolysis of anhydrous hydrofluoric acid, and purifying to obtain the product.
At present, the fluorine gas produced by the industrial preparation method of the medium temperature electrolytic method of the fluorine gas has lower purity, wherein HF and CF 4 The impurity content is higher, and the requirements of the electronic industry can be met after further purification treatment.
For example, chinese patent CN115305486a discloses an apparatus and method for preparing high purity fluorine gas, which uses the physical property that the boiling point of fluorine gas is lower than that of other impurities, and then performs primary purification, and then performs purification on fluorine gas through a secondary filter, but the purification cost is high. Chinese patent CN101423195a discloses a method for purifying fluorine gas, which uses a rectification method to control reflux ratio to purify fluorine gas, but can cause problems of liquefaction of fluorine gas due to too low temperature, and causes safety accidents.
Disclosure of Invention
In order to solve the technical problems of more energy consumption, high purification cost and possible safety accidents in the fluorine gas purification process in the related technology, the application provides a device and a method for preparing high-purity fluorine gas, which are characterized in that through the reaction of nickel fluoride tetrahydrate, potassium bifluoride and fluorine gas, the cost is lower, the energy consumption is less, the hidden danger of fluorine gas purification in the prior art is solved, and the construction safety is greatly improved.
In a first aspect, the present application provides a device for preparing high-purity fluorine gas, which adopts the following technical scheme:
a device for preparing high-purity fluorine gas comprises a reactor, a thermometer, a pressure gauge and N 2 Purging pipeline F 2 Air inlet pipeline F 2 An air outlet pipeline and a vacuumizing pipeline; the F is 2 Air inlet pipeline and N 2 The purging pipeline is arranged below the reactor and connected with the reactor through a pipeline, the F 2 The air outlet pipeline and the vacuumizing pipeline are connected above the reactor through pipelines, and the pressure gauge and the thermometer are both arranged above the reactor.
In a specific embodiment, the material of the reactor is selected from one of monel plate or nickel plate materials.
In a specific embodiment, the N 2 Purging pipeline F 2 Air inlet pipeline F 2 The material of the air outlet pipeline and the vacuumizing pipeline is one of carbon steel material, monel material and stainless steel pipe material.
In a second aspect, the present application provides a method for preparing high-purity fluorine gas, which adopts the following technical scheme:
a method for preparing high purity fluorine gas, comprising the steps of:
s1: adding nickel fluoride salt and potassium fluoride into a stirrer according to the mole ratio, heating and stirring to form a mixture, and adding the mixture into a granulator to prepare spherical particles;
s2: putting the spherical particles in the step S1 into a reactor, reacting with nitrogen-fluorine mixed gas with the fluorine gas volume content of 20-40%, forming porous particles, and vacuumizing for later use;
s3: introducing fluorine gas into the reactor, and controlling the reaction conditions to obtain K 3 NiF 7 Then, vacuumizing for standby;
s4: raising the temperature of the reactor to K 3 NiF 7 Decomposing to obtain high-purity fluorine gas.
In a specific embodiment, the molar ratio of the fluoronickel salt to potassium fluorohydride is 1 (2-6).
In a specific embodiment, in the step S1: stirring at 100-150 deg.c, cooling to 30-40 deg.c, and pelletizing the molten mixture in a pelletizer.
In a specific embodiment, the spherical particles have an average particle size of 1 to 20mm.
In a specific embodiment, the pressure of the reaction in the step S2 is 0.1-0.5Mpa, and the reaction temperature is 100-200 ℃.
In a specific embodiment, the reaction conditions in step S3 are: the reaction pressure is 0.1-0.5Mpa, the reaction temperature is 200-300 ℃, and the reaction time is 2-8h.
In a specific embodiment, the step S4 specifically includes: raising the temperature of the reactor to 350-450 ℃ and keeping for 1-8h to obtain the high-purity fluorine gas.
The application has at least one of the following beneficial effects:
1. the method prepares porous spheres by nickel fluoride tetrahydrate and potassium fluoride, especially when the particle diameter of the spherical particles is 5-20mm, and strictly controls the reaction temperature in a reactor to 200-300 ℃ and the reaction pressure to beThe reaction time of 0.1-0.5Mpa is 2-8h, so that the tetrahydrate nickel fluoride, potassium bifluoride and fluorine gas can be fully reacted to obtain K 3 NiF 7 。
2. According to the method, through the reaction of the nickel fluoride tetrahydrate, the potassium bifluoride and the fluorine gas, the production hidden danger of fluorine gas purification in the prior art is solved, the construction safety is greatly improved, and the requirement of the electronic industry on fluorine gas production is met.
3. The molar ratio of nickel fluoride tetrahydrate to potassium bifluoride is controlled to be 1: (2-6) reacting with the reaction conditions of other steps to prepare the K 3 NiF 7 No by-product is generated, and K is decomposed at the subsequent temperature of 350-450 DEG C 3 NiF 7 When the method is used, the purity of the obtained fluorine gas can reach 99.9 percent.
4. This application is through setting up the top at the reactor with the evacuation pipeline, can be with the residual gas of the reactant that the in-process of reaction produced, the abundant discharge reactor of hydrogen fluoride gas and other impurity gas of production has guaranteed reaction environment's stability.
Drawings
FIG. 1 is a schematic diagram of an apparatus for producing a high-purity fluorine gas.
Reference numerals illustrate: 1. a reactor; 2. a thermometer; 3. a pressure gauge; 4. n (N) 2 Purging the pipeline; 5. f (F) 2 An air intake duct; 6. f (F) 2 An air outlet pipe; 7. and (5) vacuumizing the pipeline.
Detailed Description
The present application is described in further detail below with reference to fig. 1 and examples.
Example 1
The embodiment 1 discloses a device for preparing high-purity fluorine gas, which comprises a reactor 1, a thermometer 2, a pressure gauge 3 and N 2 Purge pipe 4, F 2 Air intake duct 5, F 2 An air outlet pipeline 6 and a vacuumizing pipeline 7.F (F) 2 Air intake ducts 5 and N 2 The purging pipeline 4 is arranged below the reactor 1 and is connected with the reactor 1 through a pipeline, F 2 An air outlet pipeline 6 and a vacuumizing pipeline 7 are arranged above the reactor 1 and are connected through pipelines, F 2 An air intake duct 5 forDelivery of F into reactor 1 2 ，N 2 The gas inlet pipe is used for introducing N into the reactor 1 2 ，F 2 The gas outlet pipe 6 is used for introducing F generated in the reactor 1 2 To the subsequent equipment, the evacuation line 7 is used for evacuating the passage of the operating gas in the reactor 1, and the thermometer 2 is used for controlling the temperature of the reactor 1. The pressure gauge 3 is used for controlling and observing the pressure of the reactor 1, the reactors 1, N 2 Purge pipe 4, F 2 Air intake duct 5, F 2 The air outlet pipeline 6 and the vacuumizing pipeline 7 are made of Monel materials.
In the present embodiment, the reactors 1 and N 2 Purge pipe 4, F 2 Air intake duct 5, F 2 The materials of the air outlet pipeline 6 and the vacuumizing pipeline 7 are Monel materials, only optimized selection is adopted, but not only limited, other materials such as carbon steel, stainless steel and the like can be adopted, and only F prevention can be realized 2 The corrosion can be performed.
The embodiment 1 also discloses a method for preparing high-purity fluorine gas, which comprises the following steps:
s1: nickel fluoride tetrahydrate and potassium bifluoride are mixed according to a mole ratio of 1:2 adding the mixture into a stirrer for stirring, heating the mixture to 150 ℃ to form a molten mixture, uniformly stirring the mixture, cooling the mixture to 40 ℃, and pressing the mixture into spherical particles with the diameter of 20mm through a granulator for standby;
s2: putting the spherical particles in the step S1 into a reactor, vacuumizing, introducing fluorine-nitrogen mixed gas with 20% fluorine gas content, controlling the pressure to be 0.5Mpa, heating to 100 ℃, and vacuumizing for later use after the reaction is completed;
s3: introducing fluorine gas, controlling the pressure to be 0.1Mpa, raising the temperature of the reactor to 200 ℃, maintaining the state for 8 hours, and reacting to generate K 3 NiF 7 Vacuumizing the reactor for standby;
s4: the reactor temperature was raised to 350℃and maintained at this state for 8 hours to allow K in the spherical particles 3 NiF 7 Fully decomposing to release high-purity fluorine gas, and adopting infrared spectrum analysis and GC chromatographic analysis, wherein the purity of the fluorine gas is 99.996%.
Example 2
The embodiment 2 discloses a device for preparing high-purity fluorine gas, which comprises a reactor 1, a thermometer 2, a pressure gauge 3 and N 2 Purge pipe 4, F 2 Air intake duct 5, F 2 An air outlet pipeline 6 and a vacuumizing pipeline 7.F (F) 2 Air intake ducts 5 and N 2 The purging pipeline 4 is arranged below the reactor 1 and is connected with the reactor 1 through a pipeline, F 2 An air outlet pipeline 6 and a vacuumizing pipeline 7 are arranged above the reactor 1 and are connected through pipelines, F 2 The inlet pipe 5 is used for feeding F into the reactor 1 2 ，N 2 The gas inlet pipe is used for introducing N into the reactor 1 2 ，F 2 The gas outlet pipe 6 is used for introducing F generated in the reactor 1 2 To the subsequent equipment, the evacuation line 7 is used for evacuating the passage of the operating gas in the reactor 1, and the thermometer 2 is used for controlling the temperature of the reactor 1. The pressure gauge 3 is used to control and observe the pressure of the reactor 1.
The embodiment 2 also discloses a method for preparing high-purity fluorine gas, comprising the following steps:
s1: nickel fluoride tetrahydrate and potassium bifluoride are mixed according to a mole ratio of 1:6, adding the mixture into a stirrer for stirring, heating the mixture to 100 ℃ to form a molten mixture, uniformly stirring the molten mixture, cooling the mixture to 30 ℃, and pressing the mixture into spherical particles with the diameter of 5mm through a granulator for standby;
s2: putting the spherical particles in the step S1 into a reactor, vacuumizing, introducing fluorine-nitrogen mixed gas with 20% fluorine gas content, controlling the pressure to be 0.5Mpa, heating to 200 ℃, and vacuumizing for later use after the reaction is completed;
s3: introducing fluorine gas, controlling the pressure to be 0.5Mpa, raising the temperature of the reactor to 300 ℃, maintaining the state for 2 hours, and reacting to generate K 3 NiF 7 Vacuumizing the reactor for standby;
s4: the reactor temperature was raised to 450℃and maintained at this state for 2 hours to allow K in the spherical particles 3 NiF 7 Fully decomposing to release high-purity fluorine gas, and adopting infrared spectrum analysis and chromatographic analysis, wherein the purity of the fluorine gas is 99.98%.
Example 3
This example 3 discloses a process for preparing high purity fluorineThe device for gas and gas comprises a reactor 1, a thermometer 2, a pressure gauge 3 and N 2 Purge pipe 4, F 2 Air intake duct 5, F 2 An air outlet pipeline 6 and a vacuumizing pipeline 7.F (F) 2 Air intake ducts 5 and N 2 The purging pipeline 4 is arranged below the reactor 1 and is connected with the reactor 1 through a pipeline, F 2 An air outlet pipeline 6 and a vacuumizing pipeline 7 are arranged above the reactor 1 and are connected through pipelines, F 2 The inlet pipe 5 is used for feeding F into the reactor 1 2 The N is 2 The gas inlet pipe is used for introducing N into the reactor 1 2 ，F 2 The gas outlet pipe 6 is used for introducing F generated in the reactor 1 2 To the subsequent equipment, the evacuation line 7 is used for evacuating the passage of the operating gas in the reactor 1, and the thermometer 2 is used for controlling the temperature of the reactor 1. The pressure gauge 3 is used to control and observe the pressure of the reactor 1.
The embodiment 3 also discloses a method for preparing high-purity fluorine gas, which comprises the following steps:
s1: nickel fluoride tetrahydrate and potassium bifluoride are mixed according to a mole ratio of 1:4 adding the mixture into a stirrer for stirring, heating the mixture to 130 ℃ to form a molten mixture, uniformly stirring the mixture, cooling the mixture to 30 ℃, and pressing the mixture into spherical particles with the diameter of 10mm through a granulator for standby;
s2: putting the spherical particles in the step S1 into a reactor, vacuumizing, introducing fluorine-nitrogen mixed gas with 20% fluorine gas content, controlling the pressure between 0.3Mpa, heating to 150 ℃, and vacuumizing for later use after the reaction is completed;
s3: introducing fluorine gas, controlling the pressure to be 0.3Mpa, raising the temperature of the reactor to 250 ℃, maintaining the state for 6 hours, and reacting to generate K 3 NiF 7 Vacuumizing the reactor for standby;
s4: the reactor temperature was raised to between 400℃and maintained at this state for 4 hours to allow K in the spherical particles 3 NiF 7 Fully decomposing to release high-purity fluorine gas, and adopting infrared spectrum analysis and chromatographic analysis, wherein the purity of the fluorine gas is 99.9%.
Comparative example 1
A method for preparing high purity fluorine gas, comprising the steps of:
s1: nickel fluoride tetrahydrate and potassium bifluoride are mixed according to a mole ratio of 1:8, adding the mixture into a stirrer for stirring, heating the mixture to 130 ℃ to form a molten mixture, uniformly stirring the molten mixture, cooling the mixture to 30 ℃, and pressing the mixture into spherical particles with the diameter of 25mm through a granulator for standby;
s2: putting the spherical particles in the step S1 into a reactor, vacuumizing, introducing fluorine-nitrogen mixed gas with 20% fluorine gas content, controlling the pressure between 0.3Mpa, heating to 150 ℃, and vacuumizing for later use after the reaction is completed;
s3: introducing fluorine gas, controlling the pressure to be 0.3Mpa, raising the temperature of the reactor to 250 ℃, maintaining the state for 6 hours, and reacting to generate K 3 NiF 7 Vacuumizing the reactor for standby;
s4: the reactor temperature was raised to between 400℃and maintained at this state for 4 hours to allow K in the spherical particles 3 NiF 7 Fully decomposing to release high-purity fluorine gas, and adopting infrared spectrum analysis and chromatographic analysis, wherein the purity of the fluorine gas is 97.5%.
Comparative example 2
A method for preparing high purity fluorine gas, comprising the steps of: s1: nickel fluoride tetrahydrate and potassium bifluoride are mixed according to a mole ratio of 1:4, adding the mixture into a stirrer for stirring, heating the mixture to 100 ℃ to form a molten mixture, uniformly stirring the mixture, cooling the mixture to 30 ℃, and pressing the mixture into spherical particles with the diameter of 10mm through a granulator for standby;
s2: putting the spherical particles in the step S1 into a reactor, vacuumizing, introducing fluorine-nitrogen mixed gas with 20% fluorine gas content, controlling the pressure to be 0.5Mpa, heating to 200 ℃, and vacuumizing for later use after the reaction is completed;
s3: introducing fluorine gas, controlling the pressure to be 0.6Mpa, raising the temperature of the reactor to 300 ℃, maintaining the state for 2 hours, and reacting to generate K 3 NiF 7 Vacuumizing the reactor for standby;
s4: the reactor temperature was raised to 500℃and maintained at this state for 2 hours to allow K in the spherical particles 3 NiF 7 Fully decomposing to release high-purity fluorine gas, and adopting infrared spectrum analysis and chromatographic analysis, wherein the purity of the fluorine gas is 96.4%.
Comparative example 3
A method for preparing high purity fluorine gas, comprising the steps of:
s1: nickel fluoride tetrahydrate and potassium bifluoride are mixed according to a mole ratio of 1:1 adding a stirrer, stirring, heating to 130 ℃ to form a molten mixture, uniformly stirring, cooling to 30 ℃, and pressing into spherical particles with the diameter of 10mm by a granulator for standby;
s2: putting the spherical particles in the step S1 into a reactor, vacuumizing, introducing fluorine-nitrogen mixed gas with 20% fluorine gas content, controlling the pressure between 0.3Mpa, heating to 150 ℃, and vacuumizing for later use after the reaction is completed;
s3: introducing fluorine gas, controlling the pressure to be 0.3Mpa, raising the temperature of the reactor to 250 ℃, maintaining the state for 9 hours, and reacting to generate K 3 NiF 7 Vacuumizing the reactor for standby;
s4: the reactor temperature was raised to between 400℃and maintained at this state for 4 hours to allow K in the spherical particles 3 NiF 7 Fully decomposing to release high-purity fluorine gas, and adopting infrared spectrum analysis and chromatographic analysis, wherein the purity of the fluorine gas is 91.1%.
Comparative example 4
A method for preparing high purity fluorine gas, comprising the steps of:
s1: nickel fluoride tetrahydrate and potassium bifluoride are mixed according to a mole ratio of 1:4, adding the mixture into a stirrer to stir for standby;
s2: putting the spherical particles in the step S1 into a reactor, vacuumizing, introducing fluorine-nitrogen mixed gas with 20% fluorine gas content, controlling the pressure between 0.3Mpa, heating to 150 ℃, and vacuumizing for later use after the reaction is completed;
s3: introducing fluorine gas, controlling the pressure to be 0.3Mpa, raising the temperature of the reactor to 250 ℃, maintaining the state for 6 hours, and reacting to generate K 3 NiF 7 Vacuumizing the reactor for standby;
s4: the reactor temperature was raised to between 400℃and maintained at this state for 4 hours to allow K in the spherical particles 3 NiF 7 Fully decomposing to release high-purity fluorine gas, and adopting infrared spectrum analysis and chromatographic analysis, wherein the purity of the fluorine gas is 97.9%.
In the step S3 of the above examples and comparative examples, the fluorine gas used is a general fluorine gas, that is, a fluorine gas produced by electrolysis by a conventional method for producing a fluorine gas by electrolysis, which generally contains a large amount of HF, and the background of the present invention will be described in detail, and therefore, will not be described in detail here.
The applicant found that in the reaction process of the nickel fluoride salt and the potassium fluorohydride, the powdered nickel fluoride salt and the potassium fluorohydride are reacted with common fluorine gas, the fluorine gas can only react with the powder on the surface layer in the reaction process, the utilization rate of the common fluorine gas is reduced, and the reaction is not thorough, so that in order to solve the technical problem, the applicant makes the following efforts: after the nickel fluoride salt and the potassium fluoride are prepared into spherical particles, particularly when the average particle diameter is 5-20mm, uniform holes can be formed in the spherical particles through the reaction of water and fluorine gas in the spherical particles in a reactor, the reaction temperature in the reactor is strictly controlled to be 200-300 ℃ under the condition of uniform holes, the reaction pressure is 0.1-0.5Mpa, the reaction time is 2-8h, and the nickel fluoride salt and the potassium fluoride can fully react with common fluorine gas to obtain K3NiF7, and the generation of subsequent byproducts can be reduced.
The applicant found in the course of the study that K was obtained by reaction of a fluoronickel salt and potassium fluorohydride with fluorine gas 3 NiF 7 In order to solve the problem that the purity of the subsequent fluorine gas is not high enough due to the fact that a great deal of single-factor research experiments are carried out by the applicant, the applicant finds that when the nickel fluoride salt is nickel fluoride tetrahydrate and the molar ratio of the nickel fluoride salt to potassium bifluoride is 1 (2-6), the K is prepared under the conditions that the pressure of the reaction is 0.1-0.5Mpa and the temperature of the reaction is 100-200 DEG C 3 NiF 7 The yield is highest, and simultaneously, K is decomposed at 350-450 DEG C 3 NiF 7 When the method is used, the purity of the obtained fluorine gas can reach 99.9%, the technical problems in the prior art are properly solved, the purity of the fluorine gas is greatly improved, and the method has higher industrial value.
At present, the technical scheme of the application has been subjected to pilot-scale experiments, namely small-scale experiments of products before large-scale mass production; after the pilot test is completed, the use investigation of the user is performed in a small range, and the investigation result shows that the user satisfaction is higher; now, the preparation of the formal production of the product for industrialization (including early warning and investigation of intellectual property risks) is started; the above; only the preferred embodiments of the present application; the scope of protection of the present application is not limited in this regard; any person skilled in the art is within the technical scope of the disclosure of the present application; equivalent substitutions or changes are made according to the technical proposal of the application and the improved conception thereof; are intended to be encompassed within the scope of this application.
Claims (10)
1. The device for preparing the high-purity fluorine gas is characterized in that: comprises a reactor (1), a thermometer (2), a pressure gauge (3) and N 2 Purging pipeline (4), F 2 Air inlet pipeline (5), F 2 An air outlet pipeline (6) and a vacuumizing pipeline (7); the F is 2 Air inlet pipe (5) and N 2 The purging pipeline (4) is arranged below the reactor (1) and is connected with the reactor (1) through a pipeline, and the F 2 The air outlet pipeline (6) and the vacuumizing pipeline (7) are connected with each other through pipelines above the reactor (1), and the pressure gauge (3) and the thermometer (2) are both arranged above the reactor (1).
2. The apparatus for producing a high-purity fluorine gas according to claim 1, wherein: the material of the reactor (1) is selected from one of Monel plate or nickel plate materials.
3. The apparatus for producing a high-purity fluorine gas according to claim 1, wherein: the N is 2 Purging pipeline (4), F 2 Air inlet pipeline (5), F 2 The air outlet pipeline (6) and the vacuumizing pipeline (7) are made of one of carbon steel materials, monel materials and stainless steel pipe materials.
4. A method for preparing high-purity fluorine gas, comprising the steps of:
s1: adding nickel fluoride salt and potassium fluoride into a stirrer according to the mole ratio, heating and stirring to form a mixture, and adding the mixture into a granulator to prepare spherical particles;
s2: putting the spherical particles in the step S1 into a reactor (1), reacting with nitrogen-fluorine mixed gas with the fluorine gas volume content of 20-40% to form porous particles, and vacuumizing for later use;
s3: introducing fluorine gas into the reactor (1), and controlling the reaction condition to obtain K 3 NiF 7 Then, vacuumizing for standby;
s4: raising the temperature of the reactor (1) to K 3 NiF 7 Decomposing to obtain high-purity fluorine gas.
5. The method for producing a high-purity fluorine gas according to claim 4, wherein the molar ratio of the fluoronickel salt to potassium fluorohydride is 1 (2-6).
6. The method for producing high-purity fluorine gas according to claim 4, wherein in said step S1: stirring at 100-150 deg.c, cooling to 30-40 deg.c, and pelletizing the molten mixture in a pelletizer.
7. The method for producing a high-purity fluorine gas according to claim 6, wherein the spherical particles have an average particle diameter of 1 to 20mm.
8. The method for producing a high purity fluorine gas according to claim 4, wherein the pressure of the reaction in step S2 is 0.1 to 0.5Mpa and the reaction temperature is 100 to 200 ℃.
9. The method for preparing high purity fluorine gas according to claim 4, wherein the reaction conditions in step S3 are: the reaction pressure is 0.1-0.5Mpa, the reaction temperature is 200-300 ℃, and the reaction time is 2-8h.
10. The method for preparing high-purity fluorine gas according to claim 4, wherein the step S4 is specifically: raising the temperature of the reactor (1) to 350-450 ℃, and keeping the temperature for 1-8h to obtain the high-purity fluorine gas.
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