CN115490215B - Device and method for preparing nitrogen trifluoride - Google Patents
Device and method for preparing nitrogen trifluoride Download PDFInfo
- Publication number
- CN115490215B CN115490215B CN202211140607.0A CN202211140607A CN115490215B CN 115490215 B CN115490215 B CN 115490215B CN 202211140607 A CN202211140607 A CN 202211140607A CN 115490215 B CN115490215 B CN 115490215B
- Authority
- CN
- China
- Prior art keywords
- tank
- nitrogen trifluoride
- fluorine
- ammonium bifluoride
- hydrogen fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 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 98
- 238000000034 method Methods 0.000 title abstract description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 97
- 239000011737 fluorine Substances 0.000 claims abstract description 97
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 97
- 239000007789 gas Substances 0.000 claims abstract description 89
- 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 abstract description 86
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 55
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- ASZZHBXPMOVHCU-UHFFFAOYSA-N 3,9-diazaspiro[5.5]undecane-2,4-dione Chemical compound C1C(=O)NC(=O)CC11CCNCC1 ASZZHBXPMOVHCU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 23
- 230000002572 peristaltic effect Effects 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 238000010926 purge 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
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000012774 insulation material Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005868 electrolysis reaction Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000006096 absorbing agent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 4
- 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
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003682 fluorination reaction Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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
- 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
- 238000011109 contamination Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 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
- 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000012360 testing method Methods 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a device and a preparation method for preparing nitrogen trifluorideThe method adopts a mode of combining electrolysis fluorine preparation and micro reaction to prepare nitrogen trifluoride gas, firstly takes hydrogen fluoride as a raw material and potassium hydrogen fluoride as a carrier, and prepares fluorine gas through electrolysis; secondly, in a microreactor, fluorine gas and ammonia gas are melted in ammonium bifluoride [ NH ] 4 F (HF) x (x=1-5) to prepare the target product nitrogen trifluoride. Molten ammonium bifluoride [ NH ] 4 F (HF) x (x=1 to 5) is used as a heat absorber to disperse the reaction heat and is also used as NH 3 And the reaction is promoted. The production process device used by the invention is simple, low in reaction activity, high in safety and strong in operability, is suitable for large-scale production, and has wide 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 cause contamination of the surface of semiconductor materials such as silicon and silicon nitride, especially semiconductor materials having a thickness of less than 1.5 μm. With the development of nanotechnology and the large-scale development of electronic industry technology, the demand for nitrogen trifluoride will be increasing. With the improvement of the performance of electronic products, the international semiconductor industry has higher and higher requirements on the nitrogen trifluoride preparation process. General preparation of NF 3 There are two methods of gas: direct fluorine gas and electrolytic processes. The direct fluorine gas method mainly comprises fluorine reagent F 2 With NH 3 Or NH 4 HF 2 Or NH 4 F or urea. But F 2 Particularly active, complex chemical reaction, great exothermic reaction, difficult control, great content of byproducts and NF 3 The yield of (2) is less than 10%, which is not suitable for industrial production; electrolytic fluorination directly using anhydrous HF as solvent and ammonium bifluoride as raw material under mild condition to prepare NF 3 Although the electrolytic method has simple operation and low equipment cost, the electrolytic method has low yield and is not suitable for industrialized large scaleProducing a mould; the fluorine gas direct conversion method or the electrolytic fluorination method has larger equipment reactor volume, high risk coefficient and difficult control of the reaction.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide a device and a method for preparing nitrogen trifluoride, which are used for preparing nitrogen trifluoride gas by adopting a mode of combining electrolysis fluorine preparation and micro-reaction, and the device has the advantages of simple production process, low reaction activity, high safety, strong operability, suitability for large-scale production and wide application prospect.
In order to solve the technical problems, the invention adopts the following technical scheme: an apparatus for preparing nitrogen trifluoride comprises a fluorine making tank 1, a hydrogen fluoride tank 2, an ammonium bifluoride tank 3, an ammonia tank 5, a micro-reactor 6, an ammonium bifluoride collecting tank 7, a condenser 8, a nitrogen trifluoride collecting tank 9, a purifying and purifying system 10, a tail gas absorption tower 11 and a liquid nitrogen cooling device 14;
the hydrogen fluoride tank 2 is connected with the fluorine making tank 1, and a solid feed inlet is arranged on 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 the microreactor 6, the 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; the second outlet of the microreactor 6 is connected with a condenser 8; the first outlet of the condenser 8 is connected with the hydrogen fluoride tank 2, and the second outlet of the condenser 8 is connected with the 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; the nitrogen purging devices are connected to the reactors and the storage tanks, valves of different types are arranged on the pipelines, and heat insulation materials are coated on the pipelines and the devices.
Preferably, the packing material in the tail 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 mixing area and a reaction area, and the length ratio of the mixing area to the reaction area is 1: (1-5), an ammonia gas feeding hole and an ammonium bifluoride feeding hole are arranged at the inlet of the mixing area, the distance between the ammonia gas feeding hole and the ammonium bifluoride feeding hole is 1-100 mm, and the fluorine gas feeding hole is arranged at the front section of the reaction area.
Preferably, the length of the mixing zone is 100-4000 mm, and the length of the reaction zone is 100-6000 mm.
Further, a micro-separator or a theta-ring packing is provided inside the pipe of the microreactor 6.
Further, the fluorine making tank 1, the hydrogen fluoride tank 2, the ammonia tank 5 and the nitrogen trifluoride collecting tank 9 are respectively provided with a temperature indicator and a pressure indicator, and the hydrogen fluoride ammonium tank 3 and the condenser 8 are respectively provided with a temperature indicator for monitoring the temperature and the pressure of each device.
Preferably, a peristaltic pump 4 is also arranged on the connecting pipeline of the ammonium bifluoride tank 3 and the microreactor 6 and is used for controlling the input rate of molten ammonium bifluoride into the microreactor; a flow meter I12 is also arranged on the connecting pipeline of the fluorine making tank 1 and the microreactor 6 and is used for controlling the flow of fluorine gas entering the microreactor 6; the connecting pipeline of the ammonia tank 5 and the micro-reactor 6 is also provided with a flowmeter II 13 for controlling the flow of the ammonia entering the micro-reactor 6.
Further, peristaltic pumps are respectively arranged on the connecting line of the ammonium bifluoride collecting tank 7 and the ammonium bifluoride tank 3, the connecting line of the condenser 8 and the ammonium bifluoride tank, and the connecting line of the nitrogen trifluoride collecting tank 9 and the purifying and absorbing system 10.
A method for preparing nitrogen trifluoride by using the preparation device of nitrogen trifluoride, comprising the following steps:
step one: cleaning and evacuating a fluorine production tank 1, adding potassium hydrogen fluoride and hydrogen fluoride into the fluorine production tank 1 in a mass ratio of 1:1-10:1, heating the fluorine production tank 1 to 90-120 ℃, and starting to prepare fluorine gas under the condition of current of 1-100A;
step two: the switch of the peristaltic pump 4 is turned on, the speed of the peristaltic pump 4 is set to be 0.1-0.4 mol/h, and the molten ammonium bifluoride (NH) is introduced into the microreactor 6 4 F·(HF) x Opening a valve of a fluorine gas pipeline and a valve of an ammonia gas tank at the same time, inputting ammonia gas and fluorine gas into the micro-reactor 6, wherein the introducing rate of the ammonia gas flow is 0-1.5 mol/h, the introducing rate of the fluorine gas flow is 0-1.5 mol/h, 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;
after the ammonia gas and the fluorine gas react in the micro-reactor 6, the 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 out by the fluorine gas is condensed by a condenser and then enters the hydrogen fluoride tank 2 for recycling.
Step three: nitrogen trifluoride and other impurity gases are collected in the nitrogen trifluoride collecting tank 9, the temperature of the nitrogen trifluoride collecting tank 9 is reduced to minus 130 ℃ by using a liquid nitrogen cooling device 14, the nitrogen trifluoride is condensed into liquid nitrogen trifluoride, and the uncooled impurity gases enter a tail gas absorption tower 11 for absorption and then are discharged; the liquid nitrogen trifluoride enters the purifying and purifying system 10 for purifying 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 the nitrogen trifluoride can achieve quite technical progress and practicality, has wide utilization value, and has at least the following advantages:
the device for preparing the nitrogen trifluoride has the advantages of simple structure, relatively small volume, low reaction activity, mild reaction condition, easy control, high safety, strong operability, high yield of the nitrogen trifluoride, and small pollution of tail gas after absorption treatment, thereby being suitable for large-scale production and having wide application prospect.
Drawings
FIG. 1 is a process flow diagram of a method for preparing nitrogen trifluoride in accordance with the present invention.
FIG. 2 is a graph of the gas chromatography analysis of the nitrogen trifluoride product obtained in example 1 of the present invention.
FIG. 3 is a graph of the gas chromatography analysis of the nitrogen trifluoride product obtained in example 2 of the present invention.
In the figure: 1. the device comprises a fluorine making tank 2, a hydrogen fluoride tank 3, an ammonium bifluoride tank 4, a peristaltic pump 5, an ammonia tank 6, a microreactor 7, an ammonium bifluoride collecting tank 8, a condenser 9, a nitrogen trifluoride collecting tank 10, a purifying and purifying system 11, a tail gas absorption tower 12, a flowmeter I13, a flowmeter II 14 and liquid nitrogen cooling equipment
Detailed Description
In order to further describe the technical means and effects adopted by the present invention to achieve the preset purposes, the following description refers to the specific implementation, structure, characteristics and effects of an apparatus for preparing nitrogen trifluoride and a preparation method thereof according to the present invention, which are described in detail below with reference to the accompanying drawings and preferred embodiments.
The invention provides a device and a method for preparing nitrogen trifluoride, as shown in figure 1, wherein the device comprises a fluorine making tank 1, a hydrogen fluoride tank 2, an ammonium bifluoride tank 3, an ammonia tank 5, a microreactor 6, an ammonium bifluoride collecting tank 7, a condenser 8, a nitrogen trifluoride collecting tank 9, a purifying and purifying 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 is used for inputting reaction raw material hydrogen fluoride into the fluorine making tank 1; the fluorine making tank 1 is provided with a solid feed inlet 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 exhausting impurity gas generated in the electrolytic reaction and hydrogen fluoride gas carried out to the tail gas absorption tower 11 for adsorption and then exhausting; the second outlet of the fluorine making tank 1 is arranged at the anode of the fluorine making tank 1; the heating jacket is arranged outside the ammonium bifluoride tank and is used for keeping the ammonium bifluoride in the ammonium bifluoride tank in a molten state; the second outlet of the fluorine making tank 1, the ammonium bifluoride tank 3 and the ammonia tank 5 are connected with the microreactor 6 for inputting fluorine gas and ammonium bifluoride (in a molten state) [ NH ] into the microreactor 4 F·(HF) x (x=1 to 5), ammonia gas; the first outlet of the microreactor 6 is connected to an ammonium bifluoride collection tank 7 for the purpose of collecting unreacted fluorideThe ammonium bifluoride is collected to an ammonium bifluoride collection tank 7, the ammonium bifluoride collection tank 7 is also connected with an ammonium bifluoride tank 3, and a peristaltic pump is arranged on a connecting pipeline of the ammonium bifluoride collection tank 7 and the ammonium bifluoride tank 3 and is used for pumping unreacted ammonium bifluoride into the ammonium bifluoride tank 3 so that the ammonium bifluoride can be recycled; the second outlet of the micro-reactor 5 is connected with a condenser, and nitrogen trifluoride gas, hydrogen fluoride gas carried by fluorine gas, hydrogen fluoride gas and other impurity gas generated in the reaction process all pass through the condenser 8, and the hydrogen fluoride gas is condensed and liquefied in the condensation process of the condenser 8; the 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 that the hydrogen fluoride can be recycled; the second outlet of the condenser 8 is connected with a nitrogen trifluoride collecting tank 9, nitrogen trifluoride and other impurity gases can enter the nitrogen trifluoride collecting tank 9 through a pipeline, a liquid nitrogen cooling device 14 is arranged at the bottom of the nitrogen trifluoride collecting tank 9, the liquid nitrogen cooling device 14 can condense and liquefy the nitrogen trifluoride to enable the nitrogen trifluoride to exist in the nitrogen trifluoride collecting tank 9 in a liquid state, the top outlet of the nitrogen trifluoride collecting tank 9 is connected with a tail gas absorption tower 11, and impurity gases and residual uncooled hydrogen fluoride gases generated in the reaction process enter the tail gas absorption tower 11 to be absorbed and then are discharged; the bottom of the nitrogen trifluoride collecting tank 9 is provided with an outlet which is connected with the purifying and purifying system 10, a peristaltic pump is arranged on a connecting pipeline of the nitrogen trifluoride collecting tank 9 and the purifying and purifying system 10, nitrogen trifluoride liquid is pumped into the purifying and purifying system for further purifying and purifying, other miscellaneous gases except nitrogen trifluoride are removed, and the combined nitrogen trifluoride is filled after the purifying and purifying is finished. And each reactor and each storage tank are connected with nitrogen purging equipment for purging tail gas in each equipment and each pipeline after the test is stopped. Valves of different types are arranged on the pipelines for controlling the process routes, and heat-insulating materials are coated on the pipelines and the devices.
The invention is not described in detail in the section of the prior art.
Preferably, the filling material in the tail gas absorption tower 11 is an alkali metal compound, mainly sodium hydroxide, sodium peroxide, sodium fluoride and the like.
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), an ammonia gas feed inlet and an ammonium bifluoride feed inlet are arranged at the inlet of the mixing zone, the distance between the ammonia gas feed inlet and the ammonium bifluoride feed inlet is 1-100 mm, and a 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.
Further, a micro-separator or a theta-ring packing is provided inside the pipe of the microreactor 6.
Further, the fluorine making tank 1, the hydrogen fluoride tank 2, the ammonia tank 5 and the nitrogen trifluoride collecting tank 9 are respectively provided with a temperature indicator and a pressure indicator, and the hydrogen fluoride ammonium tank 3 and the condenser 8 are respectively provided with a temperature indicator for monitoring the temperature and the pressure of each device.
Preferably, peristaltic pump 4 is also provided on the connection line of ammonium bifluoride tank 3 and microreactor 6 for controlling the rate of input of molten ammonium bifluoride into the microreactor.
The connecting pipeline of the fluorine making tank 1 and the microreactor 6 is also provided with a flowmeter I12 for controlling the flow of fluorine gas entering the microreactor 6.
The connecting pipeline of the ammonia tank 5 and the micro-reactor 6 is also provided with a flowmeter II 13 for controlling the flow of the ammonia entering the micro-reactor 6.
Further, peristaltic pumps are arranged on the connecting line of the ammonium bifluoride collecting tank 7 and the ammonium bifluoride tank 3, the connecting line of the condenser 8 and the ammonium bifluoride tank, and the connecting line of the nitrogen trifluoride collecting tank 9 and the purifying and absorbing system 10, and are used for conveying various liquid substances;
the invention adopts a mode of combining electrolytic fluorine production and micro reaction to prepare nitrogen trifluoride gas, firstly takes hydrogen fluoride as a raw material and potassium hydrogen fluoride as a carrier, and carries out electrolysis to prepare fluorine gas under the conditions that the temperature of a fluorine production tank is 90-120 ℃ and the current is 1-100A; introducing the prepared fluorine gas into the micro-reactorIntroducing ammonia gas and molten ammonium bifluoride (NH) into a reactor 4 F·(HF) x X=1 to 5, and the fluorine gas and the ammonia gas are fused with NH at the temperature of 80 to 100 DEG C 4 F- (HF) x (x=1-5) to prepare target product nitrogen trifluoride with HF and N 2 ，N 2 O，CO 2 Production of impurities such as CO, recovered hydrogen fluoride and ammonium bifluoride [ NH ] 4 F·(HF) x Returning the reaction formula of (x=1-5) to the hydrogen fluoride tank and the ammonium bifluoride tank for recycling, wherein 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 making tank 1, adding 400g of potassium hydrogen fluoride into the fluorine making tank 1, evacuating the fluorine making tank 1, and then introducing 100g of hydrogen fluoride into the fluorine making tank 1; the temperature of the fluorine making tank 1 is increased to 90 ℃, and under the current of 75A, potassium hydrogen fluoride in the fluorine making tank 1 is subjected to electrolytic reaction in a hydrogen fluoride solvent to prepare fluorine gas, and the generated hydrogen gas enters the tail gas absorption tower 11. The length of the micro-reactor 6 tube is 8000mm, the tube diameter is 6mm, the length of the mixing area is 2000mm, and the length of the reaction area is 6000mm; the switch of the peristaltic pump 4 was turned on, the rate of the peristaltic pump 4 was set to 0.3mol/h, and ammonium bifluoride [ NH ] was introduced into the microreactor 6 in a molten state 4 F·(HF) 2 Simultaneously opening a valve of a fluorine gas pipeline and a valve of an ammonia gas tank, and respectively introducing fluorine gas flow and ammonia gas flow into the microreactor 6 at the speed 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 minus 25 ℃, and the reaction is started to prepare the nitrogen trifluoride. Unreacted ammonium bifluoride [ NH ] 4 F·(HF) 2 The waste water flows into an ammonium bifluoride collecting tank 7 and further flows back into the ammonium bifluoride tank; the hydrogen fluoride carried by the fluorine gas flows back to the hydrogen fluoride tank after being condensed by a condenser; nitrogen trifluorideAnd other impurity gases are collected in a nitrogen trifluoride collecting tank 9, the temperature of the nitrogen trifluoride collecting tank 9 is reduced to minus 130 ℃ by a liquid nitrogen cooling device 14, the nitrogen trifluoride is condensed into liquid nitrogen trifluoride, and then the liquid nitrogen trifluoride enters a purification system 10 for purification and filling; impurity gases generated during 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 in a condenser, 104.76g of ammonium bifluoride is obtained in an ammonium bifluoride collecting tank, and the two collecting liquids are respectively returned to the ammonium bifluoride tank 3 and the hydrogen fluoride tank 2 for recycling. The liquid nitrogen trifluoride enters the subsequent purification to obtain 106.48g of qualified nitrogen trifluoride product.
FIG. 2 is a graph of the gas chromatographic analysis of the nitrogen trifluoride product obtained in example 1, as can be seen from the figure: in addition to the main component nitrogen trifluoride, other impurity components, respectively O 2 ,N 2 ,CF 4 CO, and the like. The optimal ratio of fluorine gas to ammonia gas is 1.5:1, and the reaction yield is high.
Example 2:
cleaning the fluorine making tank 1, adding 400g of potassium hydrogen fluoride into the fluorine making tank 1, evacuating the fluorine making tank 1, and then introducing 400g of hydrogen fluoride into the fluorine making tank 1; the temperature of the fluorine making tank 1 is raised to 100 ℃, and under the current of 30A, potassium hydrogen fluoride in the fluorine making tank 1 is subjected to electrolytic reaction in a hydrogen fluoride solvent to prepare fluorine gas, and the generated hydrogen gas enters the tail gas absorption tower 11 to be absorbed. The length of the micro-reactor 6 tube is 5000mm, the diameter is 8mm, the length of the mixing area is 2000mm, and the length of the reaction area is 3000mm; the switch of the peristaltic pump 4 was turned on, the rate of the peristaltic pump 4 was set to 0.1mol/h, and ammonium bifluoride [ NH ] was introduced into the microreactor 6 in a molten state 4 F·(HF) 3 Simultaneously opening a valve of a fluorine gas pipeline and a valve of an ammonia gas tank, and respectively introducing fluorine gas flow and ammonia gas flow into the microreactor 6 at the speed 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 the nitrogen trifluoride. Unreacted ammonium bifluoride [ NH ] 4 F·(HF) 3 The waste water flows into an ammonium bifluoride collecting tank 7 and further flows back into the ammonium bifluoride tank; hydrogen fluoride carried by fluorine gas and generated during reactionThe hydrogen fluoride is condensed and flows back to the hydrogen fluoride tank after passing through the condenser; nitrogen trifluoride and other impurity gases are collected in the nitrogen trifluoride collecting tank 9, the temperature of the nitrogen trifluoride collecting tank 9 is reduced to-130 ℃ by a liquid nitrogen cooling device 14, the nitrogen trifluoride is condensed into liquid nitrogen trifluoride, and then the liquid nitrogen trifluoride enters a purification system 10 for purification; impurity gases generated during 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 through collection by a condenser, 26.19g of ammonium bifluoride is obtained in an ammonium bifluoride collecting tank, and the two collecting liquids are respectively returned to the ammonium bifluoride tank 3 and the hydrogen fluoride tank 2 for recycling. The liquid nitrogen trifluoride enters the subsequent purification to obtain 59.22g of qualified nitrogen trifluoride product.
FIG. 3 is a graph of the gas chromatographic analysis of the nitrogen trifluoride product obtained in example 2, as can be seen from the figure: in addition to the main component nitrogen trifluoride, other impurity components, respectively O 2 ，N 2 ，CF 4 CO, and the like. In example 2, the ratio of fluorine gas to ammonia gas was 2.27:1, compared with example 1, and at this time, the fluorine gas was excessively reacted, resulting in a decrease in the content of the main product and an increase in the content of the impurity components.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (7)
1. The device for preparing the nitrogen trifluoride is characterized by comprising a fluorine making tank (1), a hydrogen fluoride tank (2), an ammonium bifluoride tank (3), an ammonia tank (5), a microreactor (6), an ammonium bifluoride collecting tank (7), a condenser (8), a nitrogen trifluoride collecting tank (9), a purifying and purifying system (10), a tail gas absorbing tower (11) and liquid nitrogen cooling equipment (14);
the hydrogen fluoride tank (2) is connected with the fluorine making tank (1), and a solid feed inlet is arranged on 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 connected with the micro-reactor (6), the first outlet of the micro-reactor (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); the second outlet of the micro-reactor (6) is connected with a condenser (8); the first outlet of the condenser (8) is connected with the hydrogen fluoride tank (2), and the second outlet of the condenser (8) is connected with the nitrogen trifluoride collecting tank (9); the bottom of the nitrogen trifluoride collecting tank (9) is provided with liquid nitrogen cooling equipment (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); the nitrogen purging devices are connected to each reactor and each storage tank, valves of different types are arranged on each pipeline, and heat insulation materials are coated on each pipeline and each device;
the pipe diameter of the micro-reactor (6) is 1-50 mm, the pipe length is 100-10000 mm, the micro-reactor (6) comprises a mixing area and a reaction area, and the length ratio of the mixing area to the reaction area is 1: (1-5), wherein an ammonia gas feeding port and an ammonium bifluoride feeding port are arranged at the inlet of the mixing zone, the distance between the ammonia gas feeding port and the ammonium bifluoride feeding port is 1-100 mm, and a fluorine gas feeding port is arranged at the front section of the reaction zone; the interior of the pipeline of the micro-reactor (6) is provided with a micro-separator or theta-ring filler.
2. An apparatus for preparing nitrogen trifluoride according to claim 1, characterized in that the packing material in the tail gas absorption column (11) is an alkali metal compound.
3. An apparatus for producing nitrogen trifluoride as defined in claim 1, wherein the mixing zone has a length of 100 to 4000mm and the reaction zone has a length of 100 to 600 mm.
4. An apparatus for preparing nitrogen trifluoride according to claim 1, characterized in that the fluorine making tank (1), the hydrogen fluoride tank (2), the ammonia 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.
5. An apparatus for preparing nitrogen trifluoride according to claim 1, characterized in that the connection line of the ammonium bifluoride tank (3) and the microreactor (6) is also provided with a peristaltic pump (4); a flowmeter I (12) is also arranged on the connecting pipeline of the fluorine making tank (1) and the microreactor (6); the connecting pipeline of the ammonia tank (5) and the micro-reactor (6) is also provided with a flowmeter II (13).
6. An apparatus for preparing nitrogen trifluoride according to claim 1, characterized in that peristaltic pumps are respectively arranged on the connecting lines of the ammonium bifluoride collecting tank (7) and the ammonium bifluoride tank (3), on the connecting lines of the condenser (8) and the hydrogen fluoride tank (2), and on the connecting lines of the nitrogen trifluoride collecting tank (9) and the purifying system (10).
7. A method for producing nitrogen trifluoride by using the apparatus for producing nitrogen trifluoride as claimed in any one of claims 1 to 6, comprising the steps of:
step one: cleaning and evacuating a fluorine production tank (1), adding potassium hydrogen fluoride and hydrogen fluoride into the fluorine production tank (1) in a mass ratio of 1:1-10:1, heating the fluorine production tank (1) to 90-120 ℃, and starting to prepare fluorine gas under the condition of current of 1A-100A;
step two: opening a switch of a 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, and simultaneously opening a valve of a fluorine gas pipeline and a valve of an ammonia tank,inputting ammonia gas and fluorine gas into a micro-reactor (6), wherein the feeding rate of the ammonia gas flow is 0-1.5 mol/h, the feeding rate of the fluorine gas flow is 0-1.5 mol/h, the temperature of the micro-reactor (6) is adjusted to 80-100 ℃, the temperature of a condenser (8) is adjusted to minus 30-10 ℃, and the reaction is started to prepare nitrogen trifluoride;
after ammonia gas and fluorine gas react in the microreactor (6), the 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 out by the fluorine gas is condensed by a condenser and then enters a hydrogen fluoride tank (2) for recycling;
step three: nitrogen trifluoride and other impurity gases are collected in a nitrogen trifluoride collecting tank (9), the temperature of the nitrogen trifluoride collecting tank (9) is reduced to minus 130 ℃ by a liquid nitrogen cooling device (14), the nitrogen trifluoride is condensed into liquid nitrogen trifluoride, and the uncooled impurity gases enter a tail gas absorption tower (11) for absorption and then are discharged; and (3) the liquid nitrogen trifluoride enters a purification system (10) for purification and filling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211140607.0A CN115490215B (en) | 2022-09-20 | 2022-09-20 | Device and method for preparing nitrogen trifluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211140607.0A CN115490215B (en) | 2022-09-20 | 2022-09-20 | Device and method for preparing nitrogen trifluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115490215A CN115490215A (en) | 2022-12-20 |
| CN115490215B true CN115490215B (en) | 2024-01-30 |
Family
ID=84470073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211140607.0A Active CN115490215B (en) | 2022-09-20 | 2022-09-20 | Device and method for preparing nitrogen trifluoride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115490215B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117482864A (en) * | 2023-10-28 | 2024-02-02 | 福建德尔科技股份有限公司 | Preparation system and method of electronic grade chlorine trifluoride |
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 |
-
2022
- 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115490215A (en) | 2022-12-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115490215B (en) | Device and method for preparing nitrogen trifluoride | |
| CN100486900C (en) | Method for purifying tungsten hexafluoride | |
| CN104973629B (en) | A kind of method of purification of tungsten hexafluoride | |
| CN111039267B (en) | Device and method for prepurifying electrolytic prepared nitrogen trifluoride crude product | |
| CN110606490B (en) | Synthesis and purification method of high-purity silicon tetrafluoride | |
| US11554354B2 (en) | Micro-reaction system and method for preparing 2-methyl-4-amino-5-aminomethyl pyrimidine | |
| CN113247870B (en) | Method and device for preparing high-purity nitrogen trifluoride gas | |
| CN111085081A (en) | Device and method for removing hydrogen fluoride in fluorine gas | |
| CN1328159C (en) | Equipment and technological process for preparing nitrogen trifluoride by using ammonia and hydrogen fluoride as raw material | |
| CN101798689A (en) | Process and device for preparing nitrogen trifluoride by continuous electrolytic process | |
| CN104926597A (en) | Preparation method of pulmonic cavity ventilating liquid | |
| CN113353893B (en) | Sulfur tetrafluoride synthesis method and reaction system | |
| CN105693463A (en) | Method for preparing C2-C6 perfluoroalkane | |
| CN112661115B (en) | Separation and purification method for deep dehydration and impurity removal of FTrPSA refined by anhydrous HF produced by fluorite method | |
| CN116407913B (en) | Steam-water separation device for preparing nitrogen trifluoride and preparation system | |
| CN102863312B (en) | Preparation process of carbon tetrafluoride and device implementing same | |
| CN104693166B (en) | A kind of preparation method of metaformaldehyde | |
| CN112744788B (en) | Separation and purification method for deep dehydration and impurity removal of FTrPSA refined by anhydrous HF (hydrogen fluoride) produced by fluosilicic acid method | |
| CN105217575A (en) | A kind of reactive distillation removes the method for moisture in hydrogen fluoride | |
| CN215540754U (en) | Reaction device for high-purity chlorine trifluoride | |
| CN106220491B (en) | Production of chloroacetic acid method | |
| CN213610603U (en) | Germanium tetrachloride tail gas absorbing device | |
| CN1384049A (en) | Preparation of nitrogen trifluoride | |
| CN103121664B (en) | Production technique of high-purity hydrofluoric acid | |
| CN105152134B (en) | A kind of method and device for preparing hydrogen fluoride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |