CN114225883A - Device and method for preparing tungsten hexafluoride - Google Patents
Device and method for preparing tungsten hexafluoride Download PDFInfo
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- CN114225883A CN114225883A CN202111666269.XA CN202111666269A CN114225883A CN 114225883 A CN114225883 A CN 114225883A CN 202111666269 A CN202111666269 A CN 202111666269A CN 114225883 A CN114225883 A CN 114225883A
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- NXHILIPIEUBEPD-UHFFFAOYSA-H tungsten hexafluoride Chemical compound F[W](F)(F)(F)(F)F NXHILIPIEUBEPD-UHFFFAOYSA-H 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 147
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000010937 tungsten Substances 0.000 claims abstract description 69
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 68
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 65
- 239000011737 fluorine Substances 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 36
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 36
- 239000000126 substance Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- -1 moisture Substances 0.000 abstract description 5
- 238000003491 array Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012025 fluorinating agent Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- WQJQOUPTWCFRMM-UHFFFAOYSA-N tungsten disilicide Chemical compound [Si]#[W]#[Si] WQJQOUPTWCFRMM-UHFFFAOYSA-N 0.000 description 1
- 229910021342 tungsten silicide Inorganic materials 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 239000010969 white metal Substances 0.000 description 1
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- 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
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/242—Tubular reactors in series
-
- 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
- B01J7/00—Apparatus for generating gases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
The invention provides a device and a method for preparing tungsten hexafluoride, and relates to the technical field of electronic special gas production. The device for preparing tungsten hexafluoride provided by the invention comprises a tube array vertical reaction unit, wherein the tube array vertical reaction unit comprises a tube array vertical reactor, the tube array vertical reactor comprises at least two reaction tube arrays connected in series, a porous tray is arranged in each reaction tube array, the first reaction tube array is provided with a fluorine gas inlet, and the last reaction tube array is provided with a tungsten hexafluoride outlet; and a heating assembly coated outside the reaction tube. When the device provided by the invention is used for preparing tungsten hexafluoride, fluorine gas is input into the reaction tubes connected in series, so that the fluorine gas can be ensured to be in full contact reaction with tungsten raw materials filled in the reaction tubes, the contact area is large, and the utilization rate of the fluorine gas is high; moreover, the device has simple structure and high safety, the reactor does not need to be frequently disassembled and inspected and the tungsten raw material does not need to be supplemented, impurities such as moisture, air and the like are not easy to be introduced, and the prepared tungsten hexafluoride has high purity.
Description
Technical Field
The invention relates to the technical field of electronic special gas production, in particular to a device and a method for preparing tungsten hexafluoride.
Background
Tungsten hexafluoride (WF)6) The solid is a white crystal which is easy to deliquesce and smoke in humid air. High purity WF in the preparation of semiconductor materials6Unit operation for Chemical Vapor Deposition (CVD) and Atomic Layer Deposition (ALD) in general to produce tungsten contact plugs and tungsten silicide electrodes, in particularWSi made of it2Can be used as a wiring material in a large scale integrated circuit (LSI).
Currently, there are two main methods for industrially producing tungsten hexafluoride: (1) preparation of WF by reaction of fluorine gas as fluorinating agent with tungsten6(reaction formula is W + 3F)2→WF6) (2) by NF3As fluorinating agent to react with tungsten to prepare tungsten hexafluoride gas (the reaction formula is W +2 NF)3→WF6+N2) The reaction is generally carried out at 250-450 ℃, and the reaction temperature is high.
Tungsten is a silver-white metal exhibiting metallic luster, and the surface of tungsten is easily oxidized by oxygen in the atmosphere to form tungsten-containing oxide (W)2O3、WO2、WO3) The film of (3). The removal of the tungsten oxide film on the surface of the tungsten before the reaction of the tungsten with the fluorine gas can significantly reduce the reaction temperature of the tungsten and the fluorine gas. For example, chinese patent CN112533873A discloses a method for producing tungsten hexafluoride, which is prepared by using a reactor with a cooling water cooling jacket and an electric heater, wherein metal tungsten is pretreated in the reactor to remove tungsten oxide, and then fluorine gas is introduced to react at a temperature lower than 200 ℃ to obtain tungsten hexafluoride gas. However, when the apparatus is used for preparing tungsten hexafluoride, the contact between fluorine gas and tungsten is insufficient, and the utilization rate of fluorine gas is low.
Disclosure of Invention
In view of this, the present invention provides an apparatus and a method for preparing tungsten hexafluoride, and the apparatus provided by the present invention has a high utilization rate of fluorine gas when preparing tungsten hexafluoride.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a device for preparing tungsten hexafluoride, which comprises a tube array vertical reaction unit, wherein the tube array vertical reaction unit comprises a tube array vertical reactor, the tube array vertical reactor comprises at least two reaction tubes 3 connected in series, and a porous tray 4 is arranged in each reaction tube 3; the first reaction tube 3 is provided with a fluorine gas inlet 1, and the last reaction tube 3 is provided with a tungsten hexafluoride outlet 2;
and a heating assembly 8 coated outside the reaction tubes 3.
Preferably, the number of the reaction tubes 3 is 4-6.
Preferably, two adjacent reaction tubes 3 are connected in series through a tube connecting flange 5 and a tube connecting elbow 6.
Preferably, the tube array vertical reactor is further provided with a reactor shell 7, and the heating assembly 8 is arranged in the reactor shell 7; the reactor shell 7 is provided with a temperature measuring port 11, and the temperature measuring port 11 penetrates through the wall of the reactor shell;
the heating assembly 8 comprises a heat conducting medium.
Preferably, the apparatus comprises one or more tubular vertical reaction units connected in series.
The invention provides a method for preparing tungsten hexafluoride by adopting the device for preparing tungsten hexafluoride, which comprises the following steps:
inputting fluorine gas into a reaction tube 3 to contact with a tungsten raw material, and performing tungsten oxide removal reaction to obtain tungsten without tungsten oxide;
and carrying out chemical combination reaction on the tungsten without the tungsten oxide and continuously input fluorine gas to obtain the tungsten hexafluoride.
Preferably, the filling volume fraction of the tungsten raw material in the reaction tube array 3 is 60-90%.
Preferably, the pressure of the tungsten oxide removing reaction is 0.01-300 kPa, the temperature is 200-350 ℃, and the time of the tungsten oxide removing reaction of the tungsten metal per unit mass is 0.05-0.20 min/kg.
Preferably, the temperature of the combination reaction is 25-200 ℃.
The invention provides a device for preparing tungsten hexafluoride, which comprises a tube array vertical reaction unit, wherein the tube array vertical reaction unit comprises a tube array vertical reactor, the tube array vertical reactor is provided with at least two reaction tubes 3 connected in series, and the reaction tubes 3 are provided with porous trays 4; the first reaction tube 3 is provided with a fluorine gas inlet 1, and the last reaction tube 3 is provided with a tungsten hexafluoride outlet 2; the reaction tube 3 is externally coated with a heating component 8. When the device provided by the invention is used for preparing tungsten hexafluoride, fluorine gas is input into the reaction tubes 3 connected in series, the total length of the reaction tubes 3 is increased, the contact between the fluorine gas and tungsten is long and sufficient, and the fluorine gas utilization rate of the tube array vertical reaction unit is high; the adoption of the reaction tubes 3 connected in series can greatly prolong the replacement period of the tungsten raw material and realize the continuous operation of the device; the device provided by the invention has the advantages of simple structure, high safety and stable operation, and can continuously and automatically realize the production of high-purity tungsten hexafluoride. Frequent disassembly and inspection of the reactor and replenishment of tungsten raw materials are not needed, impurities such as moisture, air and the like are not easy to introduce, and the prepared tungsten hexafluoride is high in purity.
Further, the device provided by the invention comprises a tube array vertical reaction unit or a plurality of tube array vertical reaction units connected in series. When the device comprises more than two tube array vertical reaction units connected in series, the fluorine gas can be ensured to be fully reacted, the utilization rate of the fluorine gas is further improved, and the device has good economic value. Moreover, the tubular vertical reaction unit is combined, so that the tubular vertical reaction unit is convenient to disassemble, inspect and replace.
The invention provides a method for preparing tungsten hexafluoride by adopting the device for preparing tungsten hexafluoride, which comprises the following steps: inputting fluorine gas into a reaction tube 3 to contact with a tungsten raw material, and performing tungsten oxide removal reaction to obtain tungsten without tungsten oxide; and carrying out chemical combination reaction on the tungsten without the tungsten oxide and continuously input fluorine gas to obtain the tungsten hexafluoride. According to the preparation method provided by the invention, firstly, fluorine gas is introduced to contact with the tungsten raw material to remove tungsten oxide on the surface of the tungsten raw material, and then, fluorine gas is introduced to react, so that the reaction activity of tungsten can be obviously improved, and the reaction temperature of the fluorine gas and tungsten can be obviously reduced; fluorine gas is input into the reaction tubes 3 connected in series, so that the fluorine gas can be ensured to be in full contact reaction with the tungsten raw material filled in the reaction tubes 3, the contact area is large, and the utilization rate of the fluorine gas is high; moreover, fluorine gas is continuously input from the fluorine gas inlet 1, and the generated tungsten hexafluoride is continuously output, so that the production of high-purity tungsten hexafluoride can be continuously and automatically realized; when the device is used for producing tungsten hexafluoride, frequent disassembly and inspection of the reactor and tungsten powder supplement are not needed, impurities such as moisture, air and the like are not easy to introduce, and the prepared tungsten hexafluoride is high in purity; moreover, the method provided by the invention is simple to operate, high in safety and low in environmental pollution. As shown in the test results of the examples, the reaction efficiency of the fluorine gas in the preparation method provided by the invention is 95.5-99.3%, the yield of the tungsten hexafluoride is 99.2-99.5%, and the purity is 99.999%.
Drawings
FIG. 1 is a schematic view of the structure of an apparatus for producing tungsten hexafluoride, which is used in example 1;
FIG. 2 is a schematic view of the structure of the apparatus for preparing tungsten hexafluoride used in example 2;
in fig. 1 to 2, 1 is a fluorine gas inlet, 2 is a tungsten hexafluoride outlet, 3 is a reaction tube, 4 is a porous tray, 5 is a tube connecting flange, 6 is a tube connecting bent tube, 7 is a reactor shell, 8 is a heating assembly, 9 is a heat-conducting medium inlet, 10 is a heat-conducting medium outlet, and 11 is a temperature measuring port.
Detailed Description
The apparatus for producing tungsten hexafluoride will be described in detail with reference to fig. 1 to 2.
The invention provides a device for preparing tungsten hexafluoride, which comprises a tube array vertical reaction unit, wherein the tube array vertical reaction unit comprises a tube array vertical reactor, the tube array vertical reactor comprises at least two reaction tubes 3 connected in series, and a porous tray 4 is arranged in each reaction tube 3; the first reaction tube 3 is provided with a fluorine gas inlet 1, and the last reaction tube 3 is provided with a tungsten hexafluoride outlet 2; and a heating assembly 8 coated outside the reaction tubes 3.
The structural schematic diagram of the device for preparing tungsten hexafluoride provided by the invention is shown in fig. 1, and the detailed description is provided below with reference to fig. 1.
The tungsten hexafluoride device provided by the invention comprises a tube array vertical reaction unit, wherein the tube array vertical reaction unit comprises a tube array vertical reactor, the tube array vertical reactor comprises at least two reaction tubes 3 connected in series, and the number of the reaction tubes 3 is preferably 4-6, and more preferably 5; two adjacent reaction tubes 3 are preferably connected in series through a tube array connecting flange 5 and a tube array connecting bent tube 6; the tube array connecting flange 5 preferably comprises an upper connecting flange and a lower connecting flange, the upper connecting flange is positioned at the top of the reaction tube array 3, and the lower connecting flange is positioned at the bottom of the lower connecting flange; the upper connecting flange is detachably connected with the reaction tube array 3, and the lower connecting flange is fixedly connected or detachably connected with the reaction tube array 3; the tube array connecting flange 5 is fixedly connected or detachably connected with the tube array connecting bent tube 6; the first reaction tube 3 is provided with a fluorine gas inlet 1, and the last reaction tube 3 is provided with a tungsten hexafluoride outlet 2; the fluorine gas inlet 1 and the tungsten hexafluoride outlet 2 are preferably provided with valves. The material of the reaction tube is not particularly limited, and the reaction tube is not corroded by fluorine gas and tungsten hexafluoride, such as nickel, monel alloy, hastelloy or stainless steel.
In the invention, a porous tray 4 is arranged in the reaction tube array 3, and the porous tray 4 is used for bearing tungsten raw materials. The pore diameter of the porous tray 4 is not particularly limited in the present invention, and the tungsten material is not leaked. In the present invention, when the tungsten raw material is replaced, it is preferable that the tube array connecting flange 5 at the top of the tube array vertical reactor is opened, the tungsten raw material is fed through the open top of the reaction tube array 3, and then the tube array connecting elbow 6 is installed.
In the invention, the tube array vertical reaction unit further comprises a heating component coated outside the reaction tube array 3, and the heating component 8 is preferably a heat-conducting medium; the heat transfer medium preferably includes heat transfer oil.
In the present invention, the tube array vertical reactor is preferably provided with a reactor shell 7, and the heating assembly 8 is arranged in the reactor shell 7; the reactor shell 7 is preferably provided with a temperature measuring port 11, and the temperature measuring port 11 penetrates through the wall of the reactor shell; the reactor shell 7 is preferably further provided with a heat-conducting medium inlet 9 and a heat-conducting medium outlet 10; the heat-conducting medium inlet 9 and the heat-conducting medium outlet 10 are preferably provided with valves. The material of the reactor shell is not particularly limited in the present invention, and a metal or an alloy known to those skilled in the art may be used, specifically, stainless steel.
In the present invention, the apparatus preferably comprises one or more tubular vertical reaction units connected in series; the number of the tube array vertical reaction units is preferably 1-5.
The invention also provides a method for preparing tungsten hexafluoride by adopting the device for preparing tungsten hexafluoride, which comprises the following steps:
inputting fluorine gas into a reaction tube 3 to contact with a tungsten raw material, and performing tungsten oxide removal reaction to obtain tungsten without tungsten oxide;
and carrying out chemical combination reaction on the tungsten without the tungsten oxide and continuously input fluorine gas to obtain the tungsten hexafluoride.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention inputs fluorine gas into a reaction tube 3 to contact with tungsten raw material, and carries out tungsten oxide removing reaction to obtain tungsten without tungsten oxide.
The shape of the tungsten raw material is not particularly limited, and commercially available tungsten known to those skilled in the art can be adopted, specifically, tungsten powder, tungsten block, tungsten ingot or tungsten rod; the granularity of the tungsten powder is preferably 0.5-1500 mu m, and more preferably 100-1000 mu m; the diameters of the tungsten block and the cast ingot are preferably 0.5-10 cm independently, and more preferably 2-5 cm; the diameter of the tungsten rod is preferably 0.5-2 cm, and more preferably 1-1.5 cm. In the invention, the filling volume fraction of the tungsten raw material is preferably 60-90%, and more preferably 70-80%.
In the present invention, it is preferable to perform nitrogen substitution before the fluorine gas is fed, and the nitrogen substitution is not particularly limited in the present invention, and it is sufficient that the air in the reaction tube 3 can be completely discharged. In the invention, the temperature of the tungsten oxide removing reaction is preferably 200-350 ℃, and more preferably 250-300 ℃; the pressure of the reaction for removing tungsten oxide (i.e., the pressure of the fluorine gas) is preferably 0.01 to 300kPa, more preferably 1 to 250kPa, and still more preferably 50 to 100 kPa; the reaction time for removing tungsten oxide of tungsten metal of unit mass is preferably 0.05-0.20 min/kg, and more preferably 0.10-0.15 min/kg; in the embodiment of the present invention, when the pressure in the reaction tube 3 is significantly decreased (decreased to 50% or less of the original pressure), it indicates that the tungsten oxide reaction is occurring, and fluorine gas is continuously fed until the pressure is rapidly decreased (the pressure is rapidly decreased to the flat pressure or the slight positive pressure), and the tungsten oxide reaction is completed. In the invention, the reaction time for removing the tungsten oxide is preferably more than or equal to 1 time to ensure complete removal of tungsten oxide impurities.
After tungsten not containing tungsten oxide is obtained, the tungsten not containing tungsten oxide and fluorine gas continuously input are subjected to a chemical combination reaction to obtain tungsten hexafluoride.
In the invention, the temperature of the combination reaction is preferably 25-200 ℃, more preferably 50-150 ℃, and further preferably 60-100 ℃. The invention carries out compound reaction under the conditions, thereby not only reducing energy consumption, but also being beneficial to the stable control of the compound reaction.
After the chemical combination reaction, the present invention preferably further comprises a purification treatment of the crude tungsten hexafluoride obtained by the chemical combination reaction, and the purification treatment in the present invention is not particularly limited, and a purification treatment method of tungsten hexafluoride prepared by using fluorine gas and tungsten as raw materials, which is well known to those skilled in the art, may be adopted.
In the present invention, after the completion of the combination reaction, it is preferable to further include the steps of: stopping introducing fluorine gas into the reaction tube array 3, fully purging and replacing the fluorine gas by using nitrogen gas, cooling the tube array vertical reactor to room temperature, opening a tube array connecting flange 5 above the reaction tube array 3, adding a tungsten raw material into the reaction tube array 3 again, installing the tube array connecting flange 5, maintaining the pressure and testing leakage normally, and performing nitrogen gas replacement for later use.
The following description will be made with reference to fig. 1 for describing a specific method for preparing tungsten hexafluoride by using the apparatus for preparing tungsten hexafluoride according to the present invention, including the following steps:
adding a tungsten raw material onto a porous tray 4 in a reaction tube array 3, maintaining pressure and testing leakage normally, fully replacing with nitrogen, opening valves at a heat-conducting medium inlet 9 and a heat-conducting medium outlet 10, and introducing a heat-conducting medium into a reactor shell 7 to heat the reaction tube array 3; inputting fluorine gas into a reaction tube 3 to contact with a tungsten raw material, and performing tungsten oxide removal reaction to obtain tungsten without tungsten oxide; and (3) opening valves at a fluorine gas inlet 1 and a tungsten hexafluoride outlet 2, and continuously introducing fluorine gas and the tungsten without tungsten oxide into the reaction tube array 3 for continuous chemical combination reaction to obtain the tungsten hexafluoride.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing tungsten hexafluoride using the apparatus described in figure 1; wherein, the tube array vertical reactor comprises 4 reaction tubes connected in series.
Adding a tungsten raw material with the total mass of 600kg to a porous tray 4 in 4 serially connected reaction tubes 3, maintaining pressure and testing leakage normally, fully replacing with nitrogen, opening valves at a heat-conducting medium inlet 9 and a heat-conducting medium outlet 10, and introducing heat-conducting oil into a reactor shell 7 to heat the reaction tubes 3 to 260 ℃; and (3) inputting fluorine gas into the reaction tube array 3, keeping the pressure in the reaction tube array 3 at 200kPa after the fluorine gas is stabilized, contacting the fluorine gas with the tungsten raw material for 30min, then starting to reduce the pressure in the reaction tube array 3, and when the pressure is reduced to 50kPa, introducing a small amount of fluorine gas again, wherein the pressure in the reaction tube array 3 is rapidly reduced, which indicates that tungsten oxide impurities in the tungsten raw material are completely removed, so that tungsten without tungsten oxide is obtained.
Opening valves at a fluorine gas inlet 1 and a tungsten hexafluoride outlet 2, adjusting the temperature of heat conduction oil to 85 ℃, continuously introducing fluorine gas and tungsten without tungsten oxide into a reaction tube array 3 for continuous chemical combination reaction, after cumulatively introducing 335kg of fluorine gas, stopping introducing fluorine gas, performing full purging and replacement, reducing the temperature of the reaction tube array 3 to room temperature, opening a reverse tube array connecting flange 5, adding tungsten raw material into the reaction tube array 3 again, installing the tube array connecting flange 5, keeping pressure and testing leakage normally, performing nitrogen replacement for later use, wherein the total amount of the tungsten raw material remaining in the reaction tube array 3 is 83 kg. The obtained crude tungsten hexafluoride was collected and purified to obtain tungsten hexafluoride (830.5kg, purity 99.999%, fluorine gas reaction efficiency 95.5%, and tungsten hexafluoride yield 99.2%).
The components of the tungsten hexafluoride gas are analyzed and detected by analysis methods such as gas chromatography, mass spectrometry, infrared spectroscopy and the like, and the detection results are shown in table 1.
Example 2
Preparing tungsten hexafluoride using the apparatus described in figure 2; wherein, 2 tube array vertical reactors connected in series through a pipeline are adopted to prepare tungsten hexafluoride, and each tube array vertical reactor comprises 4 reaction tubes connected in series.
Tungsten hexafluoride was prepared according to the method of example 1, which differs from example 1 in that the total mass of the tungsten blocks in the two tubular vertical reactors was 600 kg; the reaction temperature of the compound is 85 ℃; the fluorine gas introduction was stopped after 685kg of the fluorine gas was cumulatively introduced, and the total mass of the remaining tungsten lumps was 103 kg. 1768.5kg of tungsten hexafluoride was obtained, the purity was 99.999%, the fluorine gas reaction efficiency was 99.3%, and the tungsten hexafluoride yield was 99.5%.
TABLE 1 compositional analysis results of tungsten hexafluoride prepared in examples 1-2
As can be seen from Table 1, the purity of the tungsten hexafluoride product prepared by the device provided by the invention can reach 5N level, and the fluorine gas conversion rate and the product yield are high, so that the device is suitable for industrial production.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The device for preparing the tungsten hexafluoride comprises a tube array vertical reaction unit, wherein the tube array vertical reaction unit comprises a tube array vertical reaction unit, the tube array vertical reaction unit comprises a tube array vertical reactor, the tube array vertical reactor comprises at least two reaction tubes (3) which are connected in series, and a porous tray (4) is arranged in each reaction tube (3); the first reaction tube array (3) is provided with a fluorine gas inlet (1), and the last reaction tube array (3) is provided with a tungsten hexafluoride outlet (2);
and the heating component (8) is coated outside the reaction tube array (3).
2. The device according to claim 1, wherein the number of the reaction tubes (3) is 4-6.
3. The device according to claim 2 or 3, characterized in that two adjacent reaction tubes (3) are connected in series through a tube connecting flange (5) and a tube connecting elbow (6).
4. The apparatus according to claim 1, wherein the tube array vertical reactor is further provided with a reactor housing (7), the heating assembly (8) being provided within the reactor housing (7); the reactor shell (7) is provided with a temperature measuring port (11), and the temperature measuring port (11) penetrates through the wall of the reactor shell;
the heating assembly (8) comprises a heat conducting medium.
5. The apparatus according to claim 1, 2 or 4, wherein the apparatus comprises one or more tube-in-tube vertical reaction units in series.
6. A method for preparing tungsten hexafluoride by using the apparatus for preparing tungsten hexafluoride according to any one of claims 1 to 5, including the steps of:
inputting fluorine gas into a reaction tube array (3) to contact with a tungsten raw material, and performing tungsten oxide removal reaction to obtain tungsten without tungsten oxide;
and carrying out chemical combination reaction on the tungsten without the tungsten oxide and continuously input fluorine gas to obtain the tungsten hexafluoride.
7. The method according to claim 6, wherein the packed volume fraction of tungsten feedstock in the reaction tubes (3) is 60-90%.
8. The method according to claim 6 or 7, wherein the pressure of the reaction for removing tungsten oxide is 0.01 to 300kPa, the temperature is 200 to 350 ℃, and the reaction time for removing tungsten oxide per unit mass of tungsten metal is 0.05 to 0.20 min/kg.
9. The method of claim 6, wherein the temperature of the combination reaction is 25 to 200 ℃.
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