CN101070189B - Method for preparing tungsten hexafluoride gas - Google Patents
Method for preparing tungsten hexafluoride gas Download PDFInfo
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- CN101070189B CN101070189B CN2007100621666A CN200710062166A CN101070189B CN 101070189 B CN101070189 B CN 101070189B CN 2007100621666 A CN2007100621666 A CN 2007100621666A CN 200710062166 A CN200710062166 A CN 200710062166A CN 101070189 B CN101070189 B CN 101070189B
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Abstract
The invention relates to a kind of preparation method of tungsten hexafluoride gas, mix (F2) and high purity nitrogen(N2 ) with proportion of 1:0.5-20 and add them into pyrolysis device, warm-up temperature is 10-100 degree C, pressure is 0-0.6 MPa, time used is for 1min-20min,then add them into reactor where there is raw material of wolframium (W)of 5-15Kg, the reaction temperature of fluorine gas and raw material of wolframium is between 20 degree C and 400 degree C, the reaction time is for1min-20min, fluidify and collect tungsten hexafluoride gas made in the reaction by wipe low-boiling impurity such as fluorine gas, nitrogen and nitrogen trifluoride off, after collect WF6 gas of 10kg-50kg in the low temperature collector, stop collecting it and heat up to press WF6 into carboy for keeping, using pipe to connect pyrolysis device, reactor and low temperature collector. Purity of tungsten hexafluoride gas is up to more than 99.5%.
Description
Technical field
The present invention relates to a kind of preparation method of tungsten hexafluoride.
Background technology
In the fluorochemical of tungsten, WF
6Be unique stable and by the kind of suitability for industrialized production.Its main application is as the starting material, the particularly WSi that makes with it of tungsten chemical vapor deposition (CVD) technology in electronic industry
2Can be used as the wiring material in the large-scale integrated circuit (LSI).Make the compound coating of tungsten and rhenium by the CVD technology of hybrid metal, can be used for the manufacturing of the emitting electrode and the solar collector of X-ray.In addition, WF
6Also main starting material in electron trade as semi-conducting electrode and conductive paste etc.WF
6Also have the application of many non-electronics aspect, for example make tungsten on the surface of steel, generate the surface property that hard wolfram varbide can be used to improve steel by the CVD technology.It also can be used for making some tungsten member made, as tungsten pipe and crucible etc.In addition, WF
6Also be widely used as the raw material of fluorizating agent, polymerizing catalyst and optical material etc.Be used for the exigent purity of tungsten hexafluoride of microelectronics industry super large-scale integration, be not less than 99.999%.High-purity tungsten hexafluoride generally will pass through elementary WF
6A plurality of steps such as synthetic, purification refine just can obtain.Elementary synthetic WF
6The purity quality of gas will directly influence high-purity WF
6The purity of gas.Particularly as elementary WF
6During HF too high levels in the gas, purification refine is produced high-purity WF
6The cost of gas can be very high.
Traditional method adopts common fluorine gas and tungsten powder direct reaction to prepare tungsten hexafluoride, is incorporated in the product because of containing more HF impurity in the fluorine gas, causes the tungsten hexafluoride product purity to be difficult to reach the high-purity gas requirement, and cost for purification is higher.
Summary of the invention
In order to overcome the shortcoming of prior art, the invention provides a kind of preparation method of tungsten hexafluoride, adopt to contain the HF fluorine gas seldom or the cracked gas and the tungsten powder prepared in reaction tungsten hexafluoride of nitrogen trifluoride, not only safety, and product purity height.
The present invention solves the technical scheme that its technical problem takes: with fluorine gas (F
2) and high purity nitrogen (N
2) mix in the feeding cracker by 1: 0.5～20 weight ratios, preheating temperature is 10 ℃～100 ℃, pressure is 0～0.6MPa, time is 1min～20min, after enter reactor, 5～15Kg raw material tungsten (W) is arranged in the reactor, the temperature of reaction of fluorine gas and raw material tungsten is 20 ℃～400 ℃ in the reactor, reaction times is 1min～20min, prepared tungsten hexafluoride (WF
6) gas collected by low temperature collector liquefaction, by vacuumizing removal fluorine gas, nitrogen and nitrogen trifluoride lower-boiling impurity wherein, collects the WF of 10kg～50kg in the low temperature collector
6Behind the gas, stop to collect and being warmed up to 20 ℃～100 ℃ with WF
6Gas is pressed into steel cylinder and preserves, and links to each other by pipeline between described cracker, reactor and the low temperature collector.
In order to improve the purity of product, the purity of described fluorine gas is more than 99%, wherein water (H
2O) content is below 1ppmv, and the content requirement of HF impurity is below 50ppmv, preferably below the 10ppmv.
Described fluorine gas can be used nitrogen trifluoride (NF
3) the gas replacement, NF
3The weight ratio of gas and high purity nitrogen is 1: 0.2～5.Adding high purity nitrogen is the security that guarantees building-up reactions in order to improve, and makes reaction process be easy to control.NF
3Cracking temperature is 200 ℃～600 ℃, preferred 350～500 ℃; Pressure 0MPa～0.6MPa, preferred 0.1～0.2MPa; Gas hold-up time is 1min～20min, preferred 2min～10min.
Described NF
3The purity of gas is more than 99.9%, wherein H
2The content requirement of O and HF impurity is below 5ppmv, preferably below 2ppmv.
Described raw material tungsten is particulate state or Powdered, and in order to obtain reaction effect preferably, its granularity is 1～100 order, preferred 10～50 orders; The purity of raw material tungsten helps preparing highly purified WF more than 99.9%
6Gas.
WF is collected in described low temperature collector liquefaction
6Temperature during gas is-70～0 ℃, preferred-40 ℃～-20 ℃; Pressure is-0.1～0.6MPa, and is preferred-0.099～0.2MPa, to guarantee WF
6The high collection rate of gas.
The material of described cracker and reactor is carbon steel, stainless steel, copper, nickel or Monel metal, but is the erosion resistance and the work-ing life of raising equipment, preferred nickel or Monel metal.
The material of described low temperature collector is stainless steel, copper, nickel or Monel metal, for reducing cost preferred stainless steel.
In order to reduce corrosion, the material of the pipeline between described connection cracker, reactor and the low temperature collector is nickel or Monel metal.
The WF that the present invention is prepared
6The purity of gas can reach more than 99.5%, and HF content wherein is less than 10ppmv, and help further purification and become ultra-pure gas more than 99.999%.
Description of drawings
The present invention is further described below in conjunction with drawings and Examples.
Accompanying drawing is a process flow sheet of the present invention.
Embodiment
Embodiment 1
As shown in drawings, whole preparation system is cleaned out with the method that vacuum pump 1 usefulness vacuumizes in advance.The purity of raw material fluorine gas is 99%, wherein H
2The content of O is below the 1ppmv, and the content of HF impurity is 10ppmv.Fluorine gas and high purity nitrogen enter cracker 9 by pipeline 7,8 by 1: 4 weight ratio respectively with the speed of 1L/min and carry out preheating.Preheating temperature is 80 ± 5 ℃, and working pressure is 0.2MPa, and gas hold-up time is 5min, and the back enters reactor 10 by pipeline 5.The diameter of cracker 9 is 100mm, and length is 500mm, and there is coil pipe inside, and cracker 9 usefulness Monel materials are made.The diameter of reactor 10 is 300mm, and high 600mm makes of the Monel material.Inner add in advance that purity is 99.95%, size is 80 purpose tungsten powder 10kg.The temperature of reactor 10 is 150 ± 10 ℃, and working pressure is 0.2MPa, and the fluorine gas after the preheating of coming from cracker 9 and the reaction times of tungsten powder are 5min.Synthetic WF
6Gas enters low temperature collector 11 collection of liquefying by pipeline 4.The temperature of low temperature collector 11 is-40 ± 5 ℃, and working pressure is 0.2MPa, and the foreign gas that does not liquefy emits after alkali lye is handled by evacuated tube 13,14.After reaction is carried out 20h approximately, stop to feed unstripped gas, stop preheating and building-up reactions, close the pipe valve V4 of low temperature collector 11, the temperature of low temperature collector 11 is reduced to about-70 ℃ vacuumized 1 hour with vacuum pump 1, vacuum tightness and then is warmed up to 60 ℃ with WF below 10Pa
6Gas is pressed into WF by pipeline 3
6Preserve in the gas bomb 12.
Warp is to WF
6Every impurity index is carried out analyzing and testing in the gas, and its purity is greater than 99.5%, and wherein the content of HF is 19ppmv, helps further purification and becomes ultra-pure WF
6Gas.
Embodiment 2
Whole preparation system is handled clean in advance with the method that vacuumizes, as shown in drawings.Raw material fluorine gas is replaced by gas of nitrogen trifluoride.Raw material NF
3The purity of gas is 99.9%, and wherein the content of HF and water is all below 1ppmv.Raw material NF
3Gas and high purity nitrogen feed cracker in 1: 1 ratio with the speed of 1L/min.The cracker service temperature is controlled to be 450 ± 10 ℃, and working pressure is controlled to be 0.2MPa, and the cracking time of unstripped gas in cracker is 5min, after enter reactor.Inside reactor adds in advance that purity is 99.95%, size is 80 purpose tungsten powder 10kg.Temperature of reactor is 150 ± 10 ℃, and working pressure is 0.2MPa, and the reaction times of cracked gas and tungsten powder is 5min.Synthetic WF
6The liquefaction of gas reusing low temperature collector is collected.The temperature of low temperature collector is-40 ± 5 ℃, and working pressure is 0.2MPa, and the foreign gas that does not liquefy emits after alkali lye is handled.After reaction is carried out 20h approximately, stop to feed unstripped gas, stop cracking and building-up reactions, be closed to the pipe valve of low temperature collector, the temperature of low temperature collector is reduced to about-70 ℃ vacuumized 1 hour, vacuum tightness and then heats up 60 ℃ with WF below 10Pa
6Gas is pressed into WF
6Preserve in the gas bomb.
Claims (9)
1. the preparation method of a tungsten hexafluoride, it is characterized in that: fluorine gas is mixed feeding in the cracker (9) by 1: 0.5～20 weight ratios with high purity nitrogen, preheating temperature is 10 ℃～100 ℃, pressure is 0～0.6MPa, time is 1min～20min, enter reactor (10) then, 5～15Kg raw material tungsten is arranged in the reactor (10), the temperature of reaction of fluorine gas and raw material tungsten is 20 ℃～400 ℃ in the reactor (10), reaction times is 1min～20min, prepared tungsten hexafluoride is liquefied down at-70 ℃～0 ℃ by low temperature collector (11) and collects, by vacuumizing removal fluorine gas wherein, collect the WF of 10kg～50kg in nitrogen and the nitrogen trifluoride lower-boiling impurity, low temperature collector (11)
6Behind the gas, stop to collect and being warmed up to 20 ℃～100 ℃ with WF
6Gas is pressed into steel cylinder and preserves, and links to each other by pipeline between described cracker, reactor and the low temperature collector.
2. the preparation method of tungsten hexafluoride according to claim 1, it is characterized in that: the purity of described fluorine gas is more than 99%, and wherein the content of water is below 1ppmv, and the content of HF impurity is below 50ppmv.
3. the preparation method of tungsten hexafluoride according to claim 1 is characterized in that: described fluorine gas NF
3Gas replaces, NF
3The weight ratio of gas and high purity nitrogen is 1: 0.2～5, NF
3Cracking temperature is 200 ℃～600 ℃, pressure 0MPa～0.6MPa, and gas hold-up time is 1min～20min.
4. the preparation method of tungsten hexafluoride according to claim 3 is characterized in that: described NF
3The purity of gas is more than 99.9%, wherein H
2The content requirement of O and HF impurity is below 5ppmv.
5. the preparation method of tungsten hexafluoride according to claim 1, it is characterized in that: described raw material tungsten is particulate state or Powdered, its granularity is 1～100 order; The purity of raw material tungsten is more than 99.9%.
6. the preparation method of tungsten hexafluoride according to claim 1 is characterized in that: described low temperature collector (11) liquefaction collection WF
6Temperature during gas is-70～0 ℃; Pressure is-0.1～0.6MPa.
7. the preparation method of tungsten hexafluoride according to claim 1, it is characterized in that: the material of described cracker (9) and reactor (10) is carbon steel, stainless steel, copper, nickel or Monel metal.
8. the preparation method of tungsten hexafluoride according to claim 1, it is characterized in that: the material of described low temperature collector (11) is stainless steel, copper, nickel or Monel metal.
9. the preparation method of tungsten hexafluoride according to claim 1, it is characterized in that: the material of the pipeline between described connection cracker (9), reactor (10) and the low temperature collector (11) is nickel or Monel metal.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100621666A CN101070189B (en) | 2007-06-16 | 2007-06-16 | Method for preparing tungsten hexafluoride gas |
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|---|---|---|---|
| CN2007100621666A CN101070189B (en) | 2007-06-16 | 2007-06-16 | Method for preparing tungsten hexafluoride gas |
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| CN101070189A CN101070189A (en) | 2007-11-14 |
| CN101070189B true CN101070189B (en) | 2010-08-11 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105417583B (en) * | 2015-12-31 | 2017-08-11 | 中国船舶重工集团公司第七一八研究所 | The purification devices and method of a kind of tungsten hexafluoride |
| CN105819515A (en) * | 2016-04-05 | 2016-08-03 | 张玲 | Preparation method of tungsten hexafluoride |
| CN106587159B (en) * | 2016-12-31 | 2018-09-25 | 山东飞源科技有限公司 | The preparation method of high-purity tungsten hexafluoride |
| CN106976913A (en) * | 2017-05-19 | 2017-07-25 | 江苏和福特种气体有限公司 | A kind of synthetic method of tungsten hexafluoride |
| KR102381207B1 (en) * | 2017-12-19 | 2022-04-01 | 샌트랄 글래스 컴퍼니 리미티드 | Manufacturing method of tungsten hexafluoride |
| WO2020036026A1 (en) * | 2018-08-17 | 2020-02-20 | セントラル硝子株式会社 | Method for producing tungsten hexafluoride |
| CN110510675B (en) * | 2019-08-20 | 2022-03-22 | 中船(邯郸)派瑞特种气体股份有限公司 | Continuous purification method of high-purity tungsten hexafluoride |
| CN111017945A (en) * | 2019-12-30 | 2020-04-17 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of high-purity boron trifluoride |
| CN111020619B (en) * | 2019-12-31 | 2023-10-17 | 中船(邯郸)派瑞特种气体股份有限公司 | Device and method for preparing tungsten hexafluoride gas |
| CN115974157A (en) * | 2023-02-28 | 2023-04-18 | 中船(邯郸)派瑞特种气体股份有限公司 | Preparation and purification method of molybdenum hexafluoride |
| CN117263248A (en) * | 2023-09-20 | 2023-12-22 | 湖北工业大学 | Sulfur fluorine recycling method and device for sulfur hexafluoride |
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Effective date of registration: 20190708 Address after: 057550 No. 1 Weiwu Road, Chemical Industry Agglomeration Area, Feixiang County, Handan City, Hebei Province Patentee after: CSIC (Handan) Perry Special Gas Co. Ltd Address before: 056002 No. 17 Exhibition Road, Handan City, Hebei Province Patentee before: No.718 Inst., China Shipping Heavy Industry Group Co. |
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Address after: 057550 No. five Weir Road, chemical industry gathering area, Feixiang District, Handan, Hebei, 1 Patentee after: China shipbuilding (Handan) Perry Special Gas Co.,Ltd. Address before: No.1 Weiwu Road, chemical industry gathering area, Feixiang County, Handan City, Hebei Province Patentee before: PERIC SPECIAL GASES Co.,Ltd. |