CN117303444A - Azeotropic distillation for removing MoF in tungsten hexafluoride 6 Method and apparatus of (a) - Google Patents
Azeotropic distillation for removing MoF in tungsten hexafluoride 6 Method and apparatus of (a) Download PDFInfo
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- tungsten hexafluoride
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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
- 238000010533 azeotropic distillation Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims description 13
- 239000012535 impurity Substances 0.000 claims abstract description 49
- 239000012043 crude product Substances 0.000 claims abstract description 37
- 229910015275 MoF 6 Inorganic materials 0.000 claims abstract description 19
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 28
- 238000012856 packing Methods 0.000 claims description 28
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 7
- 229910000619 316 stainless steel Inorganic materials 0.000 claims description 5
- 238000005070 sampling Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000010009 beating Methods 0.000 claims description 3
- 229910000792 Monel Inorganic materials 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000004817 gas chromatography Methods 0.000 claims description 2
- 229910000856 hastalloy Inorganic materials 0.000 claims description 2
- 238000002329 infrared spectrum Methods 0.000 claims 1
- 238000000746 purification Methods 0.000 abstract description 3
- 238000007429 general method Methods 0.000 abstract 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- WSWMGHRLUYADNA-UHFFFAOYSA-N 7-nitro-1,2,3,4-tetrahydroquinoline Chemical compound C1CCNC2=CC([N+](=O)[O-])=CC=C21 WSWMGHRLUYADNA-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/04—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/32—Other features of fractionating columns ; Constructional details of fractionating columns not provided for in groups B01D3/16 - B01D3/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/36—Azeotropic distillation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention provides an azeotropic distillation method for removing MoF in tungsten hexafluoride 6 And apparatus therefor, to contain MoF 6 Adding an entrainer into the impurity tungsten hexafluoride crude product to enable the entrainer to be matched with MoF 6 Forming azeotrope, then separating and purifying to obtain high-purity tungsten hexafluoride. The general method for purifying tungsten hexafluoride has certain requirement on the purity of crude products, and the invention adopts an azeotropic distillation method to obtain MoF of crude products 6 The mass impurity content is 0.5-2.3%, and the purification accuracy is 99.9999% at the highest.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing fine chemical separation, and particularly relates to azeotropic distillation for removing MoF in tungsten hexafluoride 6 Is provided.
Background
Tungsten hexafluoride is the only stable and industrially produced species. Its main use is as a raw material for a metal tungsten Chemical Vapor Deposition (CVD) process in the electronics industry, and particularly as a wiring material in large scale integrated circuits (LSI). In addition to its application in the electronics industry, it is also widely used in non-electronics, and the surface properties of steel can be improved by forming tungsten hard tungsten carbide on the surface of the steel by CVD techniques.
Among them, the chemical deposition (CVD) process has very high requirements for raw materials, and its product quality and product purity have a great influence on the processing of chips. With further improvement of the integration level and more precise original, the purity level of the gas and chemicals is required to be higher and higher, so as to maintain the yield of the product core. Wherein MoF 6 Melting Point and WF 6 The boiling point is very close, and the vapor pressure is very high near the melting point, so WF 6 Middle MoF 6 Difficult to remove.
The patent TW089124090 discloses a method for purifying high purity tungsten hexafluoride by contacting tungsten hexafluoride containing molybdenum hexafluoride as an impurity with a metal or alloy layer filled with the metal at 0-100 ℃ to remove the impurity in the tungsten hexafluoride, wherein the alloy layer is selected from the group consisting of metals of molybdenum, tungsten, copper, nickel, iron, cobalt, zinc, titanium, aluminum, calcium and magnesium. The method is suitable for separation and purification in a laboratory, and the large-scale production practicality of factories is poor.
Chinese patent CN105417583B discloses a purifying device and method for tungsten hexafluoride gas, which comprises a rectifying still, a rectifying column and a condenser, and can purify crude tungsten hexafluoride gas to 99.9999%. The purity of the tungsten hexafluoride crude gas is required to be 80% -90%, the crude gas needs to be primarily purified, and the cost is too high.
To sum up, the prior tungsten hexafluoride removes MoF 6 The literature is less, a batch rectifying tower or an adsorption and other technological methods are generally adopted, and the defects in efficiency and cost are obvious.
Disclosure of Invention
The invention proposes to use the impurity MoF in order to solve the defects existing in the prior art 6 Tungsten hexafluoride with the mass content of 0.5-2.3 percent is prepared by introducing entrainer and MoF 6 Forming azeotrope and separating and purifying tungsten hexafluoride.
The invention adopts the technical scheme that:
azeotropic distillation for removing MoF in tungsten hexafluoride 6 Introducing an entrainer into a tungsten hexafluoride crude product in a rectifying tower, wherein the impurity MoF in the tungsten hexafluoride crude product 6 The volume content of (2) is 0.5-2.3%, so that the entrainer and the impurity MoF are mixed 6 Forming azeotrope, and then rectifying, separating and purifying to obtain the high-purity tungsten hexafluoride.
Preferably, the entrainer is sulfur dioxide or isobutene, the sulfur dioxide and the isobutene are both in a gas phase, and the mass ratio of the tungsten hexafluoride crude product to the entrainer is 95-100:5.
Preferably, the impurity MoF in the tungsten hexafluoride crude product 6 Forming an azeotrope with an entrainer in a rectifying tower, wherein the pressure of the rectifying tower is 0.05-0.15 MPa, the temperature is 30-42 ℃, the crude product extraction amount is 10-30 kg/h, and the fine product extraction amount is 80-120 kg/h.
Preferably, the diameter of a rectifying column used for the rectifying separation rectifying tower is 100-350 mm, the height of the rectifying column is 4500-9000 mm, the packing of the rectifying column is bulk packing, the equivalent diameter of the packing is 6-8 mm, the packing height of the packing is 4000-8500 mm, and the theoretical plate number of the rectifying column is 60-180.
Preferably, in the rectification separation process, impurity gas components are continuously extracted, crude products are collected when the impurity gas components are detected to be unqualified, the crude products are re-fed into the rectification tower as raw materials, the crude products are stopped being extracted when the impurity gas components are qualified, and refined products are collected.
Preferably, in the rectification separation process, the impurity gas component is detected by gas chromatography and Fourier infrared spectroscopy;
the standard is that the volume percentage of tungsten hexafluoride is not less than 99.9999 percent;
the non-standard is that the volume percentage of tungsten hexafluoride is less than 99.9999 percent.
Azeotropic distillation for removing MoF in tungsten hexafluoride 6 The device comprises a rectifying tower, wherein a feed inlet of the rectifying tower is communicated with a raw material tank and an azeotropic tank, a discharge outlet above the rectifying tower is communicated with a feed inlet of a condenser, the discharge outlet of the condenser is communicated with a crude product tank and a fine product tank, a sampling port is arranged on the discharge outlet of the condenser, and a heater is arranged on the rectifying tower; the crude product tank is communicated with the raw material tank through a material beating pump.
Preferably, the condensation temperature of the condenser is 12 ℃;
the raw material tank stores MoF 6 Crude tungsten hexafluoride with the impurity volume content of 0.5-2.3 percent;
the azeotropic tank is provided with a heating device, and the azeotropic agent is in a gas phase;
the heater is used for heating the rectifying tower;
the sampling port is connected with a gas chromatograph and a Fourier infrared spectrometer;
the rectifying tower, the condenser, the fine product tank, the crude product tank, the pipeline and the filler are made of 316L, hastelloy or Monel.
The beneficial effects obtained by the invention are as follows:
general purification of MoF 6 And WF 6 The method is difficult to separate, and adopts an azeotropic distillation method, and crude tungsten hexafluoride MoF is obtained 6 The volume content of the impurity is 0.5 to 2.3 percent, and the purity is 99.9999 percent and the impurity MoF can be obtained 6 The volume percentage of (2) is less than or equal to 0.1X10) -6 Is a high-purity tungsten hexafluoride.
Drawings
Fig. 1 is a schematic view of the structure of the device of the present invention.
In the drawing, a 1-raw material tank, a 2-azeotropic tank, a 3-rectifying tower, a 4-cooler, a 5-crude product tank, a 6-fine product tank and a 7-heater are arranged.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to fig. 1 of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments.
Azeotropic distillation for removing MoF in tungsten hexafluoride 6 To a method comprising MoF 6 Adding an entrainer into the impurity tungsten hexafluoride crude product to enable the entrainer to be matched with MoF 6 Forming azeotrope, then separating and purifying to obtain high-purity tungsten hexafluoride. The entrainer is one of sulfur dioxide, isobutene or methylamine, and the sulfur dioxide, the isobutene or the methylamine are all in a gas phase. The mass fraction of impurities in the tungsten hexafluoride crude product is 0.5-2.3%. MoF in the tungsten hexafluoride 6 And the azeotropic agent forms an azeotrope in a rectifying tower, wherein the pressure of the rectifying tower is 0.05-0.15 MPa, and the temperature is 30-42 ℃.
Azeotropic distillation for removing MoF in tungsten hexafluoride 6 The device comprises a rectifying tower 3, wherein a feed inlet of the rectifying tower 3 is communicated with a raw material tank 1 and an azeotropic tank 2, a discharge outlet above the rectifying tower 3 is communicated with a feed inlet of a condenser 4, a discharge outlet of the condenser 4 is communicated with a raw material tank 5 and a refined material tank 6, a discharge outlet of the condenser 4 is provided with a sampling port, and a heater 7 is arranged on the rectifying tower 3; the crude product tank 5 is communicated with the raw material tank 1 through a material beating pump.
The quality requirements of the qualified products are shown in Table 1
TABLE 1 purity index (Unit:. Times.10) -6 )
| Impurity components | Impurity control index |
| MoF 6 | ≤0.1 |
| HF | ≤0.3 |
| O 2 | ≤0.1 |
| N 2 | ≤0.1 |
| CO | ≤0.1 |
| CO 2 | ≤0.1 |
| CF 4 | ≤0.1 |
| SF 6 | ≤0.1 |
| SiF 4 | ≤0.1 |
| N 2 O | ≤0.1 |
The control indexes are all volume percentages.
Example 1
Azeotropic distillation for removing MoF in tungsten hexafluoride 6 Will contain 0.5% by mass of MoF 6 Adding impurity tungsten hexafluoride crude product and sulfur dioxide into a rectifying tower 3 from the bottom of the tower, wherein the tungsten hexafluoride crude product and the sulfur dioxide areThe ratio of the amount is 95:5, sulfur dioxide is in gas phase, and the impurity components and the content are shown in table 2.
TABLE 2 impurity component content in raw materials
| Impurity components | MoF 6 | HF | O 2 | N 2 | CO | CO 2 | CF 4 | SF 6 | SiF 4 | N 2 O |
| Content/% | 0.50 | 0.3 | 0.18 | 1.85 | 0.15 | 0.28 | 0.31 | 0.29 | 0.89 | 0.58 |
The component contents are all volume contents.
The diameter of the rectifying column is 100mm, the height of the rectifying column is 4500mm, the packing of the rectifying column is bulk packing, the equivalent diameter of the packing is 6mm, the packing height of the packing is 4000mm, and the theoretical plate number of the rectifying column is 60. The material of rectifying column 3, condenser 4, top-quality jar 6, crude jar 5, pipeline and packing is 316L.
Sulfur dioxide and MoF in rectifying tower 3 6 Forming an azeotrope, wherein the pressure of the rectifying tower 3 is 0.05MPa, the temperature is 30 ℃, and the azeotrope and tungsten hexafluoride are gasified; then, tungsten hexafluoride is liquefied and refluxed through a condenser 4 of the rectifying tower 3, crude products are continuously extracted from the tower top, the extraction amount is 10kg/h, and gas chromatographic analysis and Fourier infrared spectroscopic analysis are carried out on substances extracted from the condenser at 1h intervals, wherein the impurity contents are shown in Table 3. Extracting refined tungsten hexafluoride after the purity reaches the standard, wherein the extraction amount of the refined tungsten hexafluoride is 80kg/h, and extracting tungsten hexafluoride impurity MoF 6 The content is less than or equal to 0.1 multiplied by 10 -6 The purity of tungsten hexafluoride is 99.9999%.
TABLE 3 composition and content of impurities in the rectification process
The component contents are all volume contents.
Example 2
Azeotropic distillation for removing MoF in tungsten hexafluoride 6 Is to contain 2% by mass of MoF 6 Adding the impurity tungsten hexafluoride crude product into a rectifying tower 3, and then adding isobutene from the bottom of the rectifying tower, wherein the mass ratio of the tungsten hexafluoride crude product to the isobutene is 100:5, the isobutene is in a gas phase, and the impurity components and the content are shown in Table 4.
TABLE 4 impurity component content in raw materials
| Impurity components | MoF 6 | HF | O 2 | N 2 | CO | CO 2 | CF 4 | SF 6 | SiF 4 | N 2 O |
| Content/% | 2.3 | 0.54 | 0.41 | 0.38 | 0.28 | 0.20 | 0.19 | 0.42 | 0.26 | 0.15 |
The component contents are all volume contents.
The diameter of the rectifying column is 350mm, the height of the rectifying column is 9000mm, the packing of the rectifying column is bulk packing, the equivalent diameter of the packing is 8mm, the packing height of the packing is 8500mm, and the theoretical plate number of the rectifying column is 180. The material of rectifying column 3, condenser 4, top-quality jar 6, crude jar 5, pipeline and packing is 316L.
Isobutene and MoF in rectifying column 3 6 Forming an azeotrope, wherein the pressure of the rectifying tower is 0.15MPa, the temperature is 42 ℃, and the azeotrope and tungsten hexafluoride are gasified; then, tungsten hexafluoride is liquefied and refluxed through a condenser 4 of the rectifying tower, crude products are continuously extracted from the tower top, the extraction amount is generally 30kg/h, and gas chromatographic analysis and Fourier infrared spectroscopic analysis are carried out on the substances extracted from the condenser 4 at 1h intervals, wherein the impurity contents are shown in Table 5. Extracting refined tungsten hexafluoride after the purity reaches the standard, wherein the extraction amount of the refined tungsten hexafluoride is 120kg/h, and extracting tungsten hexafluoride impurity MoF 6 The content is less than or equal to 0.1 multiplied by 10 -6 The purity of tungsten hexafluoride is 99.9999%.
TABLE 5 composition and content of impurities in rectification
The component contents are all volume contents.
Example 3
Azeotropic distillation for removing MoF in tungsten hexafluoride 6 Is prepared by mixing MoF with 1.5% by mass 6 Adding crude tungsten hexafluoride as impurity into rectifying tower 3, adding isobutene from bottom of tower, and said tungsten hexafluorideThe mass ratio of the tungsten crude product to the isobutene is 98:5, the isobutene is in a gas phase, and the impurity components and the content are shown in Table 6.
TABLE 6 impurity component content in raw materials
| Impurity components | MoF 6 | HF | O 2 | N 2 | CO | CO 2 | CF 4 | SF 6 | SiF 4 | N 2 O |
| Content/% | 1.55 | 0.68 | 1.21 | 1.35 | 0.85 | 0.75 | 0.28 | 0.74 | 0.15 | 0.25 |
The component contents are all volume contents.
The diameter of the rectifying column is 250mm, the height of the rectifying column is 7000mm, the packing of the rectifying column is bulk packing, the equivalent diameter of the packing is 7mm, the packing height of the packing is 6000mm, and the theoretical plate number of the rectifying column is 120. The material of rectifying column 3, condenser 4, top-quality jar 6, crude jar 5, pipeline and packing is 316L.
Isobutene and MoF in rectifying column 3 6 Forming an azeotrope, wherein the pressure of the rectifying tower 3 is 0.10MPa, the temperature is 35 ℃, and the azeotrope and tungsten hexafluoride are gasified; then the tungsten hexafluoride is liquefied and refluxed through a condenser of the rectifying tower 3, crude products are continuously extracted from the tower top, the general extraction amount is 25kg/h, gas chromatographic analysis and Fourier infrared spectral analysis are carried out on substances extracted from the condenser 4 at 1h time intervals, the refined tungsten hexafluoride is extracted after the purity reaches the standard, the refined extraction amount is 100kg/h, and tungsten hexafluoride impurity MoF is extracted 6 The content is less than or equal to 0.1 multiplied by 10 -6 The purity of the extracted tungsten hexafluoride reaches 99.9999 percent.
Comparative example 1
The experimental conditions of this example were the same as those of example 3, and only the type of the entrainer was changed, and methylamine was selected as the entrainer, and the impurity components and the contents are shown in Table 6.
Methylamine and MoF in rectifying tower 3 6 Forming an azeotrope, wherein the pressure of the rectifying tower 3 is 0.10MPa, the temperature is 35 ℃, and the azeotrope and tungsten hexafluoride are gasified; then the tungsten hexafluoride is liquefied and refluxed by a condenser of a rectifying tower 3, crude products are continuously extracted from the tower top, the extraction amount is generally 25kg/h, gas chromatographic analysis and Fourier infrared spectral analysis are carried out on substances extracted from the condenser 4 at 1h time intervals, wherein the impurity contents are shown in table 7, the refined tungsten hexafluoride is extracted after the purity reaches the standard, the refined extraction amount is 100kg/h, and the tungsten hexafluoride impurity is extractedMoF 6 The content is less than or equal to 0.2 multiplied by 10 -6 The purity of the extracted tungsten hexafluoride only reaches 99.999 percent.
TABLE 7 composition and content of impurities in rectification
The component contents are all volume contents.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (8)
1. Azeotropic distillation for removing MoF in tungsten hexafluoride 6 Is characterized in that: introducing an entrainer into a tungsten hexafluoride crude product in a rectifying tower, wherein an impurity MoF in the tungsten hexafluoride crude product 6 The volume content of (2) is 0.5-2.3%, so that the entrainer and the impurity MoF are mixed 6 Forming azeotrope, and then rectifying, separating and purifying to obtain the high-purity tungsten hexafluoride.
2. An azeotropic distillation to remove MoF from tungsten hexafluoride according to claim 1 6 Is characterized in that: the entrainer is sulfur dioxide or isobutene, the sulfur dioxide and the isobutene are both in a gas phase, and the mass ratio of the tungsten hexafluoride crude product to the entrainer is 95-100:5.
3. An azeotropic distillation to remove MoF from tungsten hexafluoride according to claim 1 6 Is characterized in that: the pressure of the rectifying tower is 0.05-0.15 MPa, the temperature is 30-42 ℃, the crude product extraction amount is 10-30 kg/h, and the refined product extraction amount is 80-120 kg/h.
4. An azeotropic distillation to remove MoF from tungsten hexafluoride according to claim 1 6 Is characterized in that: the diameter of a rectifying column used for rectifying and separating the rectifying tower is 100-350 mm, the height of the rectifying column is 4500-9000 mm, the packing of the rectifying column is bulk packing, the equivalent diameter of the packing is 6-8 mm, the packing filling height of the packing is 4000-8500 mm, and the theoretical plate number of the rectifying column is 60-180.
5. An azeotropic distillation to remove MoF from tungsten hexafluoride according to claim 1 6 Is characterized in that: in the rectification separation process, impurity gas components are continuously extracted, crude products are collected when the impurity gas components are detected to be unqualified, the crude products are re-fed into a rectification tower as raw materials, the crude products are stopped being extracted when the impurity gas components are qualified, and refined products are collected.
6. The method for removing MoF from tungsten hexafluoride by azeotropic distillation according to claim 5 6 Is characterized in that: in the rectification separation process, the extracted impurity gas component is detected by gas chromatography and Fourier infrared spectrum;
the standard is that the volume percentage of tungsten hexafluoride is not less than 99.9999 percent;
the non-standard is that the volume percentage of tungsten hexafluoride is less than 99.9999 percent.
7. An azeotropic distillation to remove MoF from tungsten hexafluoride according to any one of claims 1-6 6 Is characterized in that: the device comprises a rectifying tower (3), wherein a feed inlet of the rectifying tower (3) is communicated with a raw material tank (1) and an azeotropic tank (2), a discharge outlet above the rectifying tower (3) is communicated with a feed inlet of a condenser (4), a discharge outlet of the condenser (4) is communicated with a crude product tank (5) and a fine product tank (6), a discharge outlet of the condenser (4) is provided with a sampling port, and a heater (7) is arranged on the rectifying tower (3); the crude product tank (5) is communicated with the raw material tank (1) through a material beating pump.
8. An azeotropic distillation to remove MoF from tungsten hexafluoride according to claim 7 6 Is characterized in that: the condensation temperature of the condenser is 12 ℃;
the raw material tank (1) stores MoF 6 Impurity volumeCrude tungsten hexafluoride with the content of 0.5-2.3 percent;
the azeotropic tank (2) stores an azeotropic agent, the azeotropic tank (2) is provided with a heating device, and the azeotropic agent is in a gas phase;
the heater (7) is used for heating the rectifying tower (3);
the sampling port is connected with a gas chromatograph and a Fourier infrared spectrometer;
the rectifying tower (3), the condenser (4), the fine product tank (6), the crude product tank (5), the pipeline and the filler are made of 316L, hastelloy or Monel.
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