CN115490215A - Device and method for preparing nitrogen trifluoride - Google Patents
Device and method for preparing nitrogen trifluoride Download PDFInfo
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- CN115490215A CN115490215A CN202211140607.0A CN202211140607A CN115490215A CN 115490215 A CN115490215 A CN 115490215A CN 202211140607 A CN202211140607 A CN 202211140607A CN 115490215 A CN115490215 A CN 115490215A
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- tank
- nitrogen trifluoride
- fluorine
- microreactor
- ammonium bifluoride
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- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 91
- 239000011737 fluorine Substances 0.000 claims abstract description 91
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 91
- 239000007789 gas Substances 0.000 claims abstract description 86
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002360 preparation method Methods 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 80
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000000746 purification Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- 238000010521 absorption reaction Methods 0.000 claims description 25
- 239000012535 impurity Substances 0.000 claims description 19
- 230000002572 peristaltic effect Effects 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 238000005253 cladding Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 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 abstract description 8
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 239000006163 transport media Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 5
- 238000003682 fluorination reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910017855 NH 4 F Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 101100314150 Caenorhabditis elegans tank-1 gene Proteins 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/083—Compounds containing nitrogen and non-metals and optionally metals containing one or more halogen atoms
- C01B21/0832—Binary compounds of nitrogen with halogens
Abstract
The invention relates to a device and a method for preparing nitrogen trifluoride, wherein a nitrogen trifluoride gas is prepared by combining electrolysis fluorine preparation and micro reaction, and firstly, fluorine gas is prepared by electrolysis by taking hydrogen fluoride as a raw material and potassium hydrogen fluoride as a carrier; secondly, in the microreactor, fluorine gas and ammonia gas are melted into ammonium hydrogen fluoride [ NH ] 4 F (HF) x (x = 1-5) to prepare the target product nitrogen trifluoride. Molten ammonium hydrogen fluoride [ NH ] 4 F (HF) x (x =1 to 5) serves as both a heat absorber for dispersing the heat of reaction and NH 3 The transport medium of (2) promotes the reaction. The production process device used by the invention is simple, low in reaction activity, high in safety, strong in operability, suitable for large-scale production and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of chemical engineering, and particularly relates to a device and a method for preparing nitrogen trifluoride.
Background
Nitrogen trifluoride is an excellent plasma etching gas in the microelectronics industry, and does not contaminate the surface when etching semiconductor materials such as silicon and silicon nitride, particularly semiconductor materials having a thickness of less than 1.5 μm. With receivingWith the development of rice technology and the large-scale development of electronic industry technology, the demand of nitrogen trifluoride will increase. With the improvement of the performance of electronic products, the international semiconductor industry has higher and higher requirements on the preparation process of nitrogen trifluoride. General preparation of NF 3 There are two methods of gas: direct fluorine methods and electrolysis methods. Direct fluorine processes are based primarily on fluorine reagents F 2 And NH 3 Or NH 4 HF 2 Or NH 4 F or urea. But F 2 Particularly active, complex chemical reaction, much exothermic reaction, difficult control, more by-product content and NF 3 The yield is less than 10 percent, and the method is not suitable for industrial production; the electrolytic fluorination method directly uses anhydrous HF as a solvent and ammonium bifluoride as a raw material to carry out electrolytic fluorination under mild conditions to prepare NF 3 Although the electrolysis method is simple to operate and low in equipment cost, the electrolysis method is low in product yield and is not suitable for industrial large-scale production; both the fluorine direct fluorination method and the electrolytic fluorination method have the disadvantages of large volume of the reactor, high danger coefficient and difficult control of the reaction.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide a device and a method for preparing nitrogen trifluoride.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a device for preparing nitrogen trifluoride comprises a fluorine preparation tank 1, a hydrogen fluoride tank 2, an ammonium bifluoride tank 3, an ammonia gas tank 5, a microreactor 6, an ammonium bifluoride collecting tank 7, a condenser 8, a nitrogen trifluoride collecting tank 9, a purification and purification system 10, a tail gas absorption tower 11 and liquid nitrogen cooling equipment 14;
the hydrogen fluoride tank 2 is connected with the fluorine making tank 1, and a solid feeding hole is formed in the fluorine making tank 1; the fluorine making tank 1 is also provided with a cathode and an anode, a first outlet of the fluorine making tank 1 is arranged at the cathode of the fluorine making tank 1 and is connected with the tail gas absorption tower 11, and a second outlet of the fluorine making tank 1 is arranged at the anode of the fluorine making tank 1;
the second outlet of the fluorine making tank 1, the ammonium bifluoride tank 3 and the ammonia tank 5 are all connected with a microreactor 6, the first outlet of the microreactor 6 is connected with an ammonium bifluoride collecting tank 7, and the ammonium bifluoride collecting tank 7 is also connected with the ammonium bifluoride tank 3; a second outlet of the microreactor 6 is connected with a condenser 8; a first outlet of the condenser 8 is connected with the hydrogen fluoride tank 2, and a second outlet of the condenser 8 is connected with a nitrogen trifluoride collecting tank 9; the bottom of the nitrogen trifluoride collecting tank 9 is provided with a liquid nitrogen cooling device 14, the top of the nitrogen trifluoride collecting tank 9 is provided with an outlet which is connected with a tail gas absorption tower 11, and the bottom of the nitrogen trifluoride collecting tank 9 is provided with an outlet which is connected with a purification system 10; all be connected with nitrogen gas on each reactor and the storage tank and sweep equipment, all be equipped with the valve of different models on each pipeline, all the cladding has insulation material on each pipeline and each equipment.
Preferably, the packing material in the off-gas absorption tower 11 is an alkali metal compound.
Further, the pipe diameter of the micro-reactor is 1-50 mm, the pipe length is 100-10000 mm, the micro-reactor comprises a material mixing area and a reaction area, and the length ratio of the material mixing area to the reaction area is 1: (1-5), an ammonia gas feed inlet and an ammonium bifluoride feed inlet are arranged at the inlet of the material mixing zone, the distance between the ammonia gas feed inlet and the ammonium bifluoride feed inlet is 1-100 mm, and the fluorine gas feed inlet is arranged at the front section of the reaction zone.
Preferably, the length of the mixing zone is 100-4000 mm, and the length of the reaction zone is 100-6000 mm.
Furthermore, a micro partition plate or theta ring packing is arranged inside the channel of the microreactor 6.
Furthermore, a temperature indicator and a pressure indicator are respectively arranged on the fluorine preparation tank 1, the hydrogen fluoride tank 2, the ammonia gas tank 5 and the nitrogen trifluoride collecting tank 9, and a temperature indicator is respectively arranged on the ammonium bifluoride tank 3 and the condenser 8 for monitoring the temperature and the pressure of each device.
Preferably, a peristaltic pump 4 is further arranged on a connecting pipeline between the ammonium bifluoride tank 3 and the microreactor 6, and is used for controlling the input rate of the molten ammonium bifluoride into the microreactor; a connecting pipeline between the fluorine-making tank 1 and the microreactor 6 is also provided with a flowmeter I12 for controlling the flow of the fluorine gas entering the microreactor 6; and a flow meter II 13 is also arranged on a connecting pipeline between the ammonia tank 5 and the microreactor 6 and is used for controlling the flow of the ammonia gas entering the microreactor 6.
Furthermore, a peristaltic pump is respectively arranged on a connecting pipeline between the ammonium bifluoride collecting tank 7 and the ammonium bifluoride tank 3, a connecting pipeline between the condenser 8 and the hydrogen fluoride tank, and a connecting pipeline between the nitrogen trifluoride collecting tank 9 and the purification and absorption system 10.
A method for preparing nitrogen trifluoride using the apparatus for preparing nitrogen trifluoride, comprising the steps of:
the method comprises the following steps: cleaning and evacuating the fluorine preparation tank 1, adding 1 to 1 mass ratio of potassium hydrogen fluoride to hydrogen fluoride into the fluorine preparation tank 1, raising the temperature of the fluorine preparation tank 1 to 90-120 ℃, and starting to prepare fluorine gas under the condition of current 1-100A;
step two: opening a switch of the peristaltic pump 4, setting the speed of the peristaltic pump 4 to be 0.1-0.4 mol/h, and introducing molten ammonium bifluoride (NH) into the microreactor 6 4 F·(HF) x (x =1 to 5), simultaneously opening a valve of a fluorine gas pipeline and a valve of an ammonia gas tank, inputting ammonia gas and fluorine gas into the microreactor 6, adjusting the introducing speed of the ammonia gas flow to be 0 to 1.5mol/h, adjusting the introducing speed of the fluorine gas flow to be 0 to 1.5mol/h, adjusting the temperature of the microreactor 6 to be 80 to 100 ℃, adjusting the temperature of the condenser 8 to be-30 to 10 ℃, and starting to react to prepare nitrogen trifluoride;
after ammonia gas and fluorine gas react in the microreactor 6, redundant ammonium bifluoride enters an ammonium bifluoride collecting tank 7 to be collected, and then enters an ammonium bifluoride tank 3 to be recycled; the hydrogen fluoride carried over by the fluorine gas and the hydrogen fluoride generated in the reaction process are condensed by a condenser and then enter a hydrogen fluoride tank 2 for recycling.
Step three: collecting nitrogen trifluoride and other impurity gases in a nitrogen trifluoride collecting tank 9, reducing the temperature of the nitrogen trifluoride collecting tank 9 to-130 ℃ by using liquid nitrogen cooling equipment 14, condensing the nitrogen trifluoride into liquid nitrogen trifluoride, and discharging the uncooled impurity gases after the uncooled impurity gases enter a tail gas absorption tower 11 for adsorption; the liquid nitrogen trifluoride enters the purification system 10 for purification and then filling.
Compared with the prior art, the invention has obvious advantages and beneficial effects. By means of the technical scheme, the preparation method of nitrogen trifluoride can achieve considerable technical progress and practicability, has wide utilization value, and at least has the following advantages:
the device for preparing nitrogen trifluoride provided by the invention has the advantages of simple structure, relatively small volume, low reaction activity, mild reaction conditions, easiness in control, high safety, strong operability, high yield of nitrogen trifluoride and small pollution of tail gas after absorption treatment, so that the device is suitable for large-scale production and has wide application prospect.
Drawings
FIG. 1 is a process flow diagram of a method for preparing nitrogen trifluoride according to the present invention.
FIG. 2 is a gas chromatography analysis chart of a nitrogen trifluoride product obtained in example 1 of the present invention.
FIG. 3 is a gas chromatography analysis chart of a nitrogen trifluoride product obtained in example 2 of the present invention.
In the figure: 1. fluorine preparation tank 2, hydrogen fluoride tank 3, ammonium bifluoride tank 4, peristaltic pump 5, ammonia tank 6, microreactor 7, ammonium bifluoride collection tank 8, condenser 9, nitrogen trifluoride collection tank 10, purification and purification system 11, tail gas absorption tower 12, flowmeter I13, flowmeter II 14 and liquid nitrogen cooling equipment
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given of the embodiments, structures, characteristics and effects of an apparatus and a method for preparing nitrogen trifluoride according to the present invention with reference to the accompanying drawings and preferred embodiments.
The invention provides a device and a method for preparing nitrogen trifluoride, and the device comprises a fluorine preparation tank 1, a hydrogen fluoride tank 2, an ammonium bifluoride tank 3, an ammonia gas tank 5, a microreactor 6, an ammonium bifluoride collecting tank 7, a condenser 8, a nitrogen trifluoride collecting tank 9, a purification system 10, a tail gas absorption tower 11 and liquid nitrogen cooling equipment 14, as shown in figure 1. Hydrogen fluoride tank 2 and fluorine production tank1 is connected with a fluorine preparation tank 1 for inputting reaction raw material hydrogen fluoride; the fluorine making tank 1 is provided with a solid feeding hole for adding solid reaction raw material potassium hydrogen fluoride into the fluorine making tank 1; the fluorine making tank 1 is also provided with a cathode and an anode, and a first outlet of the fluorine making tank 1 is arranged at the cathode of the fluorine making tank 1 and is connected with the tail gas absorption tower 11, and is used for discharging impurity gas generated in the electrolytic reaction and hydrogen fluoride gas brought out to the tail gas absorption tower 11 for adsorption and then emptying; a second outlet of the fluorine making tank 1 is arranged at the anode of the fluorine making tank 1; the heating sleeve is arranged outside the ammonium bifluoride tank and used for keeping the ammonium bifluoride in the ammonium bifluoride tank in a molten state; a second outlet of the fluorine-making tank 1, the ammonium bifluoride tank 3 and the ammonia gas tank 5 are all connected with the microreactor 6 and used for inputting fluorine gas, (in a molten state) ammonium bifluoride [ NH ] into the microreactor 4 F·(HF) x -x =1 to 5, ammonia gas; a first outlet of the microreactor 6 is connected with an ammonium bifluoride collecting tank 7 and is used for collecting unreacted ammonium bifluoride to the ammonium bifluoride collecting tank 7, the ammonium bifluoride collecting tank 7 is also connected with the ammonium bifluoride tank 3, and a peristaltic pump is arranged on a connecting pipeline of the ammonium bifluoride collecting tank 7 and the ammonium bifluoride tank 3 and is used for pumping the unreacted ammonium bifluoride into the ammonium bifluoride tank 3 so that the ammonium bifluoride can be recycled; a second outlet of the microreactor 5 is connected with a condenser, nitrogen trifluoride gas generated in the reaction process, hydrogen fluoride gas carried by fluorine gas, hydrogen fluoride gas generated in the reaction process and other impurity gases pass through the condenser 8, and the hydrogen fluoride gas is condensed and liquefied through the condensation process of the condenser 8; a first outlet of the condenser 8 is connected with the hydrogen fluoride tank 2, and a peristaltic pump is arranged on a connecting pipeline between the condenser 8 and the hydrogen fluoride tank 2 and used for conveying condensed hydrogen fluoride liquid into the hydrogen fluoride tank 2 so as to recycle the hydrogen fluoride; a second outlet of the condenser 8 is connected with a nitrogen trifluoride collecting tank 9, nitrogen trifluoride and other impurity gases are introduced into the nitrogen trifluoride collecting tank 9 through a pipe, a liquid nitrogen cooling device 14 is provided at the bottom of the nitrogen trifluoride collecting tank 9, the liquid nitrogen cooling device 14 condenses and liquefies the nitrogen trifluoride to be present in the nitrogen trifluoride collecting tank 9 in a liquid state, a top outlet of the nitrogen trifluoride collecting tank 9 is connected with an off-gas absorption column 11, and impurity gases and the remaining impurities generated during the reaction are introduced into the nitrogen trifluoride collecting tank 9The residual hydrogen fluoride gas which is not cooled enters a tail gas absorption tower 11 to be absorbed and then is discharged; an outlet formed in the bottom of the nitrogen trifluoride collecting tank 9 is connected with the purification system 10, a peristaltic pump is arranged on a connecting pipeline between the nitrogen trifluoride collecting tank 9 and the purification system 10, nitrogen trifluoride liquid is pumped into the purification system for further purification, other miscellaneous gases except nitrogen trifluoride are removed, and qualified nitrogen trifluoride is filled after purification is finished. And nitrogen purging equipment is connected to each reactor and each storage tank and is used for purging tail gas in each equipment and each pipeline after the test is stopped. Valves with different types are arranged on each pipeline and used for controlling each process route, and each pipeline and each device are coated with heat insulation materials.
Parts of the invention not described in detail are as of prior art.
Preferably, the filling material in the tail gas absorption tower 11 is alkali metal compound, mainly sodium hydroxide, sodium peroxide, sodium fluoride, etc.
Further, the pipe diameter of the micro-reactor is 1-50 mm, the pipe length is 100-10000 mm, the micro-reactor comprises a mixing area and a reaction area, and the length ratio of the mixing area to the reaction area is 1: (1-5), the ammonia gas feed inlet and the ammonium bifluoride feed inlet are arranged at the inlets of the material mixing zone, the distance between the ammonia gas feed inlet and the ammonium bifluoride feed inlet is 1-100 mm, and the fluorine gas feed inlet is arranged at the front section of the reaction zone.
Preferably, the length of the mixing zone is 100-4000 mm, and the length of the reaction zone is 100-6000 mm.
Furthermore, a micro partition plate or a theta ring packing is arranged inside the tube of the microreactor 6.
Furthermore, a temperature indicator and a pressure indicator are respectively arranged on the fluorine preparation tank 1, the hydrogen fluoride tank 2, the ammonia gas tank 5 and the nitrogen trifluoride collecting tank 9, and a temperature indicator is respectively arranged on the ammonium bifluoride tank 3 and the condenser 8 for monitoring the temperature and the pressure of each device.
Preferably, a peristaltic pump 4 is further provided in a connection line between the ammonium acid fluoride tank 3 and the microreactor 6 for controlling the input rate of the molten ammonium acid fluoride into the microreactor.
And a flow meter I12 is also arranged on a connecting pipeline between the fluorine-making tank 1 and the microreactor 6 and is used for controlling the flow of the fluorine gas entering the microreactor 6.
And a flow meter II 13 is also arranged on a connecting pipeline between the ammonia tank 5 and the microreactor 6 and is used for controlling the flow of the ammonia gas entering the microreactor 6.
Further, peristaltic pumps are arranged on a connecting pipeline between the ammonium bifluoride collecting tank 7 and the ammonium bifluoride tank 3, a connecting pipeline between the condenser 8 and the hydrogen fluoride tank, and a connecting pipeline between the nitrogen trifluoride collecting tank 9 and the purification and absorption system 10, and are used for conveying liquid substances;
the invention prepares nitrogen trifluoride gas by combining electrolysis fluorine preparation and micro reaction, firstly, takes hydrogen fluoride as raw material and potassium hydrogen fluoride as carrier, and prepares fluorine gas by electrolysis under the conditions that the temperature of a fluorine preparation tank is 90-120 ℃ and the current is 1-100A; introducing the prepared fluorine gas into a microreactor, and simultaneously introducing ammonia gas and molten ammonium bifluoride [ NH ] 4 F·(HF) x [ x =1 to 5 ] is a process for producing molten NH containing fluorine gas and ammonia gas at a temperature of 80 to 100 ℃ 4 The target product nitrogen trifluoride is prepared by the reaction in F (HF) x (x = 1-5) accompanied by HF, N 2 ，N 2 O，CO 2 Production of impurities such as CO, recovered hydrogen fluoride and ammonium hydrogen fluoride [ NH ] 4 F·(HF) x The (x = 1-5) returns to the hydrogen fluoride tank and the ammonium bifluoride tank for recycling, and the reaction formula is as follows:
2HF→H 2 +F 2
NH 4 F·(HF) x +3F 2 →NF 3 +(x+4)HF
2NH 4 F·(HF) x +3F 2 →N 2 +(2x+8)HF
NH 4 F·(HF) x +NF 3 →N 2 +(x+4)HF
example 1:
cleaning the fluorine preparation tank 1, adding 400g of potassium hydrogen fluoride into the fluorine preparation tank 1, evacuating the fluorine preparation tank 1, and then introducing 100g of hydrogen fluoride into the fluorine preparation tank 1; the temperature of the fluorine making tank 1 is raised to 90 ℃, and potassium hydrogen fluoride in fluorine in the fluorine making tank 1 is carried out under the current of 75AThe hydrogen hydride solvent is subjected to an electrolytic reaction to prepare fluorine gas, and the generated hydrogen gas enters the tail gas absorption tower 11. The length of a microreactor 6 tube is 8000mm, the diameter of the microreactor 6 tube is 6mm, the length of a mixing region is 2000mm, and the length of a reaction region is 6000mm; opening a switch of a peristaltic pump 4, setting the speed of the peristaltic pump 4 at 0.3mol/h, and introducing molten ammonium bifluoride [ NH ] into the microreactor 6 4 F·(HF) 2 The valve of the fluorine gas line and the valve of the ammonia gas tank are opened at the same time, and the fluorine gas flow and the ammonia gas flow are respectively introduced into the microreactor 6 at the speeds of 1.12mol/h and 0.75 mol/h. The temperature of the microreactor is adjusted to 90 ℃, the temperature of the condenser 8 is adjusted to-25 ℃, and the reaction is started to prepare nitrogen trifluoride. Unreacted ammonium bifluoride [ NH ] 4 F·(HF) 2 Flows into an ammonium bifluoride collection tank 7 and further flows back into the ammonium bifluoride tank; the hydrogen fluoride carried by the fluorine gas and the hydrogen fluoride generated in the reaction process are condensed and flow back to the hydrogen fluoride tank after passing through the condenser; collecting nitrogen trifluoride and other impurity gases in a nitrogen trifluoride collecting tank 9, reducing the temperature of the nitrogen trifluoride collecting tank 9 to-130 ℃ by using liquid nitrogen cooling equipment 14, condensing the nitrogen trifluoride into liquid nitrogen trifluoride, and then filling the liquid nitrogen trifluoride after the nitrogen trifluoride is purified and purified in a purification and purification system 10; impurity gases generated in the reaction process and uncooled hydrogen fluoride gas enter the tail gas absorption tower 11 to be absorbed. After the reaction is carried out for 240min, 50g of hydrogen fluoride is obtained by collecting with a condenser, 104.76g of ammonium bifluoride is obtained in an ammonium bifluoride collecting tank, and the two kinds of collecting liquid are respectively returned to the ammonium bifluoride tank 3 and the hydrogen fluoride tank 2 for cyclic utilization. The liquid nitrogen trifluoride enters into subsequent purification and purification to obtain 106.48g of qualified nitrogen trifluoride product.
FIG. 2 is a gas chromatographic analysis of the nitrogen trifluoride product obtained in example 1, from which it can be seen that: in addition to the main component nitrogen trifluoride, there are other impurity components, each of which is O 2 ,N 2 ,CF 4 CO, etc. The ratio of fluorine gas to ammonia gas is preferably 1.5, and the reaction yield is high.
Example 2:
cleaning the fluorine preparation tank 1, adding 400g of potassium hydrogen fluoride into the fluorine preparation tank 1, evacuating the fluorine preparation tank 1, and then introducing 400g of hydrogen fluoride into the fluorine preparation tank 1; the temperature of the fluorine production tank 1When the temperature is raised to 100 ℃, potassium hydrogen fluoride in the fluorine preparation tank 1 is subjected to an electrolytic reaction in a hydrogen fluoride solvent under the current of 30A to prepare fluorine gas, and the generated hydrogen gas enters the tail gas absorption tower 11 to be absorbed. The length of the microreactor 6 is 5000mm, the diameter of the microreactor is 8mm, the length of the mixing zone is 2000mm, and the length of the reaction zone is 3000mm; opening a switch of the peristaltic pump 4, setting the speed of the peristaltic pump 4 to be 0.1mol/h, and introducing molten ammonium bifluoride [ NH ] into the microreactor 6 4 F·(HF) 3 Simultaneously, a valve of a fluorine gas pipeline and a valve of an ammonia gas tank are opened, and a fluorine gas flow and an ammonia gas flow are respectively introduced into the microreactor 6 at the speeds of 0.68mol/h and 0.3 mol/h. The temperature of the microreactor is adjusted to 100 ℃, the temperature of the condenser 8 is adjusted to-5 ℃, and the reaction is started to prepare nitrogen trifluoride. Unreacted ammonium bifluoride [ NH ] 4 F·(HF) 3 Flows into an ammonium bifluoride collection tank 7 and further flows back into the ammonium bifluoride tank; the hydrogen fluoride carried out by the fluorine gas and the hydrogen fluoride generated in the reaction process are condensed and flow back to the hydrogen fluoride tank after passing through a condenser; collecting nitrogen trifluoride and other impurity gases in a nitrogen trifluoride collecting tank 9, reducing the temperature of the nitrogen trifluoride collecting tank 9 to-130 ℃ by using liquid nitrogen cooling equipment 14, condensing the nitrogen trifluoride into liquid nitrogen trifluoride, and then entering a purification system 10 for purification; impurity gases generated in the reaction process and uncooled hydrogen fluoride gas enter the tail gas absorption tower 11 to be absorbed. After the reaction is carried out for 180min, 98g of hydrogen fluoride is obtained by the collection of a condenser, 26.19g of ammonium bifluoride is obtained in an ammonium bifluoride collection tank, and the two kinds of collection liquid are respectively returned to the ammonium bifluoride tank 3 and the hydrogen fluoride tank 2 for cyclic utilization. The liquid nitrogen trifluoride enters into subsequent purification and purification to obtain 59.22g of qualified nitrogen trifluoride product.
FIG. 3 is a gas chromatographic analysis of the nitrogen trifluoride product obtained in example 2, from which it can be seen that: in addition to the main component nitrogen trifluoride, there are other impurity components, each O 2 ，N 2 ，CF 4 CO, etc. In example 2, the ratio of fluorine gas to ammonia gas was 2.27 in comparison with example 1, and at this time, the fluorine gas was excessively reacted to cause a side reaction, resulting in a decrease in the content of main products and an increase in the content of impurity components.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and are not listed. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (9)
1. The device for preparing nitrogen trifluoride is characterized by comprising a fluorine preparation tank (1), a hydrogen fluoride tank (2), an ammonium bifluoride tank (3), an ammonia gas tank (5), a microreactor (6), an ammonium bifluoride collecting tank (7), a condenser (8), a nitrogen trifluoride collecting tank (9), a purification system (10), a tail gas absorption tower (11) and liquid nitrogen cooling equipment (14);
the hydrogen fluoride tank (2) is connected with the fluorine production tank (1), and a solid feeding port is arranged on the fluorine production tank (1); the fluorine making tank (1) is also provided with a cathode and an anode, a first outlet of the fluorine making tank (1) is arranged at the cathode of the fluorine making tank (1) and is connected with the tail gas absorption tower (11), and a second outlet of the fluorine making tank (1) is arranged at the anode of the fluorine making tank (1);
a second outlet of the fluorine making tank (1), the ammonium bifluoride tank (3) and the ammonia gas tank (5) are connected with the microreactor (6), a first outlet of the microreactor (6) is connected with the ammonium bifluoride collecting tank (7), and the ammonium bifluoride collecting tank (7) is also connected with the ammonium bifluoride tank (3); a second outlet of the microreactor (6) is connected with a condenser (8); a first outlet of the condenser (8) is connected with the hydrogen fluoride tank (2), and a second outlet of the condenser (8) is connected with a nitrogen trifluoride collecting tank (9); the bottom of the nitrogen trifluoride collecting tank (9) is provided with a liquid nitrogen cooling device (14), the top of the nitrogen trifluoride collecting tank (9) is provided with an outlet which is connected with a tail gas absorption tower (11), and the bottom of the nitrogen trifluoride collecting tank (9) is provided with an outlet which is connected with a purification system (10); all be connected with nitrogen gas on each reactor and the storage tank and sweep equipment, all be equipped with the valve of different models on each pipeline, all the cladding has insulation material on each pipeline and each equipment.
2. The apparatus for producing nitrogen trifluoride according to claim 1, wherein the packing material in the off-gas absorption column (11) is an alkali metal compound.
3. The apparatus for producing nitrogen trifluoride according to claim 1, wherein the microreactor (6) has a tube diameter of 1 to 50mm and a tube length of 100 to 10000mm, and the microreactor (6) comprises a mixing zone and a reaction zone in a ratio of the lengths of the mixing zone and the reaction zone of 1: (1-5), an ammonia gas feed inlet and an ammonium bifluoride feed inlet are arranged at the inlet of the mixing area, the distance between the ammonia gas feed inlet and the ammonium bifluoride feed inlet is 1-100 mm, and the fluorine gas feed inlet is arranged at the front section of the reaction area.
4. The apparatus for producing nitrogen trifluoride according to claim 3, wherein the length of said mixing zone is 100 to 4000mm, and the length of said reaction zone is 100 to 6000mm.
5. The apparatus for producing nitrogen trifluoride according to claim 1, wherein the microreactor (6) has a minute partition or a theta-ring packing inside its conduit.
6. An apparatus for producing nitrogen trifluoride according to claim 1, wherein the fluorine producing tank (1), the hydrogen fluoride tank (2), the ammonia gas tank (5) and the nitrogen trifluoride collecting tank (9) are each provided with a temperature indicator and a pressure indicator, respectively, and the ammonium bifluoride tank (3) and the condenser (8) are each provided with a temperature indicator, respectively.
7. The apparatus for producing nitrogen trifluoride according to claim 1, wherein a peristaltic pump (4) is further provided in a connection line between the ammonium acid fluoride tank (3) and the microreactor (6); a connecting pipeline between the fluorine making tank (1) and the microreactor (6) is also provided with a flowmeter I (12); a flow meter II (13) is also arranged on a connecting pipeline of the ammonia tank (5) and the microreactor (6).
8. The apparatus for producing nitrogen trifluoride according to claim 1, wherein a peristaltic pump is provided in each of the line connecting the ammonium acid fluoride collecting tank (7) and the ammonium acid fluoride tank (3), the line connecting the condenser (8) and the hydrogen fluoride tank (2), and the line connecting the nitrogen trifluoride collecting tank (9) and the purification absorption system (10).
9. A method for preparing nitrogen trifluoride using the apparatus for preparing nitrogen trifluoride, comprising the steps of:
the method comprises the following steps: cleaning and evacuating the fluorine preparation tank (1), adding 1;
step two: opening a switch of the peristaltic pump (4), setting the speed of the peristaltic pump (4) to be 0.1-0.4 mol/h, and introducing molten ammonium bifluoride (NH) into the microreactor (6) 4 F·(HF) x (x = 1-5), simultaneously opening a valve of a fluorine gas pipeline and a valve of an ammonia gas tank, inputting ammonia gas and fluorine gas into a micro-reactor (6), adjusting the temperature of the micro-reactor (6) to 80-100 ℃, adjusting the temperature of a condenser (8) to-30-10 ℃ and starting to react to prepare nitrogen trifluoride, wherein the introducing speed of the ammonia gas flow is 0-1.5 mol/h, and the introducing speed of the fluorine gas flow is 0-1.5 mol/h;
after ammonia gas and fluorine gas react in the microreactor (6), redundant ammonium bifluoride enters an ammonium bifluoride collecting tank (7) to be collected, and then enters an ammonium bifluoride tank (3) to be recycled; the hydrogen fluoride carried by the fluorine gas and the hydrogen fluoride generated in the reaction process are condensed by a condenser and then enter a hydrogen fluoride tank (2) for recycling.
Step three: collecting nitrogen trifluoride and other impurity gases in a nitrogen trifluoride collecting tank (9), reducing the temperature of the nitrogen trifluoride collecting tank (9) to-130 ℃ by using liquid nitrogen cooling equipment (14), condensing the nitrogen trifluoride into liquid nitrogen trifluoride, and discharging the uncooled impurity gases after the uncooled impurity gases enter a tail gas absorption tower (11) for adsorption; and the liquid nitrogen trifluoride enters a purification system (10) for purification and then is filled.
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| US6010605A (en) * | 1995-10-17 | 2000-01-04 | Florida Scientific Laboratories Inc. | Nitrogen trifluoride production apparatus |
| CN1727278A (en) * | 2005-07-27 | 2006-02-01 | 中国船舶重工集团公司第七一八研究所 | Equipment and technological process for preparing nitrogen trifluoride by using ammonia and hydrogen fluoride as raw material |
| CN101798689A (en) * | 2010-03-18 | 2010-08-11 | 黎明化工研究院 | Process and device for preparing nitrogen trifluoride by continuous electrolytic process |
| CN102101654A (en) * | 2010-08-30 | 2011-06-22 | 天津市泰旭物流有限公司 | Technology for preparing nitrogen trifluoride by molten salt direct fluorination method |
| CN103896223A (en) * | 2012-12-31 | 2014-07-02 | 天津市泰旭物流有限公司 | Device for preparing nitrogen trifluoride by virtue of direct fluorination of fused salt |
| CN114572944A (en) * | 2021-12-23 | 2022-06-03 | 西安近代化学研究所 | Preparation method of nitrogen trifluoride and nitrogen trifluoride mixed gas |
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- 2022-09-20 CN CN202211140607.0A patent/CN115490215B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6010605A (en) * | 1995-10-17 | 2000-01-04 | Florida Scientific Laboratories Inc. | Nitrogen trifluoride production apparatus |
| CN1727278A (en) * | 2005-07-27 | 2006-02-01 | 中国船舶重工集团公司第七一八研究所 | Equipment and technological process for preparing nitrogen trifluoride by using ammonia and hydrogen fluoride as raw material |
| CN101798689A (en) * | 2010-03-18 | 2010-08-11 | 黎明化工研究院 | Process and device for preparing nitrogen trifluoride by continuous electrolytic process |
| CN102101654A (en) * | 2010-08-30 | 2011-06-22 | 天津市泰旭物流有限公司 | Technology for preparing nitrogen trifluoride by molten salt direct fluorination method |
| CN103896223A (en) * | 2012-12-31 | 2014-07-02 | 天津市泰旭物流有限公司 | Device for preparing nitrogen trifluoride by virtue of direct fluorination of fused salt |
| CN114572944A (en) * | 2021-12-23 | 2022-06-03 | 西安近代化学研究所 | Preparation method of nitrogen trifluoride and nitrogen trifluoride mixed gas |
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