WO2010050342A1 - Procédé et système pour purifier du trifluorure d’azote contenant un halogène ou un composé halogéné en tant qu’impureté - Google Patents

Procédé et système pour purifier du trifluorure d’azote contenant un halogène ou un composé halogéné en tant qu’impureté Download PDF

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Publication number
WO2010050342A1
WO2010050342A1 PCT/JP2009/067399 JP2009067399W WO2010050342A1 WO 2010050342 A1 WO2010050342 A1 WO 2010050342A1 JP 2009067399 W JP2009067399 W JP 2009067399W WO 2010050342 A1 WO2010050342 A1 WO 2010050342A1
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nitrogen trifluoride
vol
halogen
chlorine
contact
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PCT/JP2009/067399
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English (en)
Japanese (ja)
Inventor
亜紀応 菊池
勇 毛利
知之 平岡
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セントラル硝子株式会社
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Publication of WO2010050342A1 publication Critical patent/WO2010050342A1/fr

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    • 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
    • C01B21/0835—Nitrogen trifluoride
    • C01B21/0837—Purification

Definitions

  • the present invention relates to a method and system for purifying nitrogen trifluoride containing halogen or a halogen compound as an impurity.
  • the gas used in the semiconductor manufacturing process is generally supplied in a form filled in a container such as a gas cylinder.
  • These source gases usually have 5 vol.
  • hydrogen halide of about ppm or more is contained as an impurity, which causes troubles due to corrosion of manufacturing equipment such as gas supply pipes and defective products due to etching of semiconductor thin films.
  • contamination of halogen impurities in gases used in semiconductor manufacturing processes is a very serious problem, and it is necessary to reduce the concentration of hydrogen halide, which is an impurity, together with the purpose of preventing corrosion and defective products described above. It is desired to be removed.
  • Non-Patent Document 1 a method using a purification agent such as zeolite for purification of nitrogen trifluoride used in a semiconductor cleaning gas.
  • Patent Document 2 a method using a hydrochloric acid aqueous solution and water as a purification method for hydrogen chloride containing a fluorine-based compound (Patent Document 1), and a method using a reducing agent aqueous solution as a method for removing NO x have been reported. (Patent Document 2).
  • An object of the present invention is to provide a purification method and system capable of efficiently and inexpensively removing impurities by suppressing the generation of halogen oxides in the purification of nitrogen trifluoride containing halogen or a halogen compound as an impurity.
  • the step of bringing the nitrogen trifluoride into contact with water and the step of bringing the nitrogen trifluoride into contact with an aqueous base solution
  • a method for purifying nitrogen trifluoride comprising contacting the nitrogen trifluoride with a reducing agent aqueous solution.
  • a nitrogen trifluoride purification system containing halogen or a halogen compound as an impurity, means for bringing the nitrogen trifluoride into contact with water, and means for bringing the nitrogen trifluoride into contact with an aqueous base
  • a system for purifying nitrogen trifluoride comprising means for bringing the nitrogen trifluoride into contact with the reducing agent aqueous solution.
  • FIG. 1 is a schematic system diagram of a nitrogen trifluoride purification system according to an embodiment of the present invention.
  • nitrogen trifluoride containing halogen or a halogen compound as an impurity is purified by contacting with water, an aqueous base solution, or an aqueous reducing agent solution.
  • the configuration of the purification system is not particularly limited as long as the nitrogen trifluoride gas to be purified can be brought into contact with each of the three aqueous solutions of water, an aqueous base solution, and an aqueous reducing agent solution, and the purification device such as a gas purifier or a cleaning device Can be used arbitrarily to construct a purification system.
  • a bubbler device, a scrubber device or the like can be used.
  • countercurrent contact As the contact method between the gas to be purified and the aqueous solution, countercurrent contact or cocurrent contact can be used. However, in consideration of the gas-liquid contact efficiency, countercurrent contact is preferred.
  • the impurities to be removed by purification include halogens such as fluorine, chlorine, bromine and iodine, chlorine fluoride, chlorine trifluoride, chlorine pentafluoride, bromine fluoride, bromine trifluoride, bromine pentafluoride and iodine fluoride.
  • halogen compounds such as iodine pentafluoride and iodine heptafluoride. Among them, it is particularly effective for fluorine, chlorine, chlorine fluoride, and chlorine trifluoride.
  • the order in which the gas to be purified is brought into contact with the aqueous solution is not particularly limited. However, considering that it is possible to remove the halogen oxide generated in contact with water and in contact with the aqueous base solution, and further considering the efficiency of purification, it is preferable to contact with the reducing agent aqueous solution. In this case, with regard to the order of contact with water and contact with the aqueous base solution, halogen hydride is generated in contact with water, but since this can be removed by contact with the reducing agent aqueous solution in a later step, the order is not limited. The effect is obtained regardless of which one is performed first.
  • contact with an aqueous base solution is more preferable than contact with an aqueous base solution, because contact with an aqueous base solution has better chlorine removal efficiency and can remove halogen hydride.
  • a halogen oxide or a hydrogen hydride is generated during the purification process of the present invention, the effect of absorption of the halogen or halogen compound is greater. The effect of improving the purity of nitrogen fluoride is sufficiently obtained.
  • the base used in the aqueous base solution is preferably an inorganic base that does not react with nitrogen trifluoride.
  • potassium salt is particularly preferable in consideration of the solubility of the fluoride salt formed after the reaction.
  • the pH of the aqueous base solution is preferably 8 or more, more preferably 9 to 11, and still more preferably 11. This is because the purification efficiency under a certain temperature is improved by increasing the pH.
  • the contact reaction temperature with the aqueous base solution is not particularly specified.
  • the reducing agent used in the reducing agent aqueous solution is preferably one that does not react with nitrogen trifluoride when the standard electrode potential in the aqueous solution is ⁇ 0.092 V or less.
  • the lower the standard electrode potential the higher the effect.
  • the compounds described in the Dictionary of Chemistry can be mentioned.
  • potassium dithionite is particularly preferred, and potassium sulfite is particularly preferred.
  • a base is allowed to coexist in the reducing agent aqueous solution when used.
  • the effect of the coexisting base has a role of preventing deterioration of the reducing agent due to the acid generated after the reduction, and as the kind of base, those that do not directly react with nitrogen trifluoride and the reducing agent are preferable.
  • potassium salt is particularly preferable in consideration of the solubility of the fluoride salt formed after the reaction.
  • the mixing ratio of the coexisting base and reducing agent is not particularly limited.
  • the contact reaction temperature with the reducing agent aqueous solution Since it is considered that the purification capacity is lowered above the temperature at which the reducing agent decomposes, use at a temperature below the temperature at which the reducing agent decomposes is preferred.
  • a temperature below the temperature at which the reducing agent decomposes For example, in the case of potassium dithionite, the use at 60 ° C. or lower is desirable.
  • the concentration of the reducing agent is, for example, when potassium dithionite is used, and the lower limit of concentration is preferably 0.29 mol / l or less, and if it is less than that, sufficient purification ability cannot be exhibited.
  • the upper limit of the concentration of the reducing agent is not limited because a sufficient purification ability is exhibited even at 1.63 mol / l which is a saturated solution.
  • Example 1 The purification system of FIG. 1 was used to purify nitrogen trifluoride containing halogen and a halogen compound as impurities.
  • the purification system includes a cylinder 1 filled with a gas to be purified, a mass flow controller 2 that controls the flow rate of the gas to be purified to a predetermined value, and a wet purification device that causes the gas to be purified to contact with the reaction liquids 4, 9, and 14. It was composed of 5, 10, and 15.
  • the wet refining apparatuses 5, 10, 15 are packed towers 7, 12, 17 filled with a filler, liquid tanks 3, 8, 13 for storing reaction liquids 4, 9, 14, and liquid tanks 3, 8, 13
  • the liquids 6, 11, and 16 for feeding the reaction liquids 4, 9, and 14 above the packing material are respectively provided, and the gas to be purified is introduced from below the packed towers 7, 12, and 17, 7, 12, 17 in countercurrent contact with the reaction liquids 4, 9, 14 and discharged from the upper part of the packed towers 7, 12, 17. That is, the gas to be purified is introduced into the wet purification device 5 and brought into countercurrent contact with the reaction solution 4, then introduced into the wet purification device 10 and brought into countercurrent contact with the reaction solution 9, and further into the wet purification device 15. It was introduced and brought into countercurrent contact with the reaction solution 14. Thereafter, the gas released from the wet purification apparatus 15 was collected in the empty container 18.
  • the mass flow controller 2 was used to control the gas flow to 274 ml / min.
  • a SUS316-made packed tower 7 made of polytetrafluoroethylene having a length of 750 cm and an inner diameter of 25 mm was used, a 2 ⁇ polytetrafluoroethylene Raschig ring was used as a filler, and water was used as a reaction solution 4. .
  • a packed column 12 made of polyvinyl chloride having a length of 1500 cm and an inner diameter of 50 mm is used, a 6 mm SUS304 helipac as a filler, and a concentration of potassium dithionite as a reaction solution 14 is 1.5 mol / l, An aqueous solution having a potassium hydroxide concentration of 0.15 mol / l was used.
  • Halogen components (chloride ions, fluoride ions, chlorite ions, chlorate ions) in the collected gas are analyzed with an infrared spectrophotometer (Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography) The purity of the purified nitrogen trifluoride gas was measured, and as a result of analysis by ion chromatography, chloride ion, fluoride ion, chlorite ion, and chlorate ion were detected at the lower limit of detection (chloride, fluoride ion).
  • the purification treatment was performed under the same conditions as in Example 1 except that a mixed gas adjusted to% was used.
  • the collected gas was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000) and ion chromatography in the same manner as in Example 1.
  • IG-1000 infrared spectrophotometer
  • Chlorite ion, and chlorate ion are below the lower limit of detection (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), and infrared
  • chloride, fluoride ion: 1 mass ppm or less chlorite, chlorate ion: 0.2 mass ppm or less
  • infrared As a result of analysis with a spectrophotometer, no peaks other than nitrogen trifluoride were confirmed, and it was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass. did.
  • the purification treatment was performed under the same conditions as in Example 1 except that an aqueous solution having 5 mol / l and a potassium carbonate concentration of 0.15 mol / l was used.
  • the collected gas was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000) and ion chromatography in the same manner as in Example 1.
  • IG-1000 infrared spectrophotometer
  • chloride ions and fluoride ions were analyzed.
  • Chlorite ion, and chlorate ion are below the lower limit of detection (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), and infrared
  • chloride, fluoride ion: 1 mass ppm or less chlorite, chlorate ion: 0.2 mass ppm or less
  • infrared As a result of analysis with a spectrophotometer, no peaks other than nitrogen trifluoride were confirmed, and it was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass. did.
  • the collected gas was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000) and ion chromatography in the same manner as in Example 1.
  • IG-1000 infrared spectrophotometer
  • chloride ions and fluoride ions were analyzed.
  • Chlorite ion, and chlorate ion are below the lower limit of detection (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), and infrared spectroscopy
  • chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less chloride, fluoride ion: 1 mass ppm or less
  • chlorite, chlorate ion 0.2 mass ppm or less
  • infrared spectroscopy As a result of analysis by a photometer, no peaks other than nitrogen trifluoride were confirmed, and it was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass. .
  • the collected gas was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000) and ion chromatography in the same manner as in Example 1.
  • IG-1000 infrared spectrophotometer
  • chloride ions and fluoride ions were analyzed.
  • Chlorite ion, and chlorate ion are below the lower limit of detection (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), and infrared
  • chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less chloride, fluoride ion: 1 mass ppm or less
  • chlorite, chlorate ion 0.2 mass ppm or less
  • infrared As a result of analysis with a spectrophotometer, no peaks other than nitrogen trifluoride were confirmed, and it was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to at least 99.999% by mass. did.
  • the collected gas was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000) and ion chromatography in the same manner as in Example 1.
  • IG-1000 infrared spectrophotometer
  • chloride ions and fluoride ions were analyzed.
  • Chlorite ion, and chlorate ion are below the lower limit of detection (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), and infrared spectroscopy
  • chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less chloride, fluoride ion: 1 mass ppm or less
  • chlorite, chlorate ion 0.2 mass ppm or less
  • infrared spectroscopy As a result of analysis by a photometer, no peaks other than nitrogen trifluoride were confirmed, and it was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass. .
  • IG-1000 infrared spectrophotometer
  • Chlorite ion, and chlorate ion are below the lower limit of detection (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), and infrared spectroscopy
  • chloride, fluoride ion: 1 mass ppm or less chlorite, chlorate ion: 0.2 mass ppm or less
  • infrared spectroscopy As a result of analysis by a photometer, no peaks other than nitrogen trifluoride were confirmed, and it was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass. .
  • the collected gas was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd.
  • the collected gas was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd.
  • chloride ions were found to be 5. 3 mass ppm, 6.1 mass ppm of fluorine ions were confirmed, and chlorite ions and chlorate ions were confirmed to be below the lower limit of detection (chlorite, chlorate ions: 0.2 mass ppm or less).
  • chlorite, chlorate ions 0.2 mass ppm or less.
  • Table 1 describes the composition of the gas to be purified used in Examples 1 to 11 and Comparative Examples 1 and 2, and the main conditions of the wet purification apparatus.
  • Table 2 lists the analysis results.
  • nitrogen trifluoride containing halogen or a halogen compound can be purified at low cost and with higher purity.
  • the present invention for example, as a purification means in the production of chloride gas or fluoride gas, or exhaust gas from semiconductor factories or chemical factories using chloride gas or fluoride gas. It can be used as an abatement means.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Gas Separation By Absorption (AREA)

Abstract

L'invention concerne un procédé de purification de trifluorure d'azote qui contient un halogène ou un composé halogéné en tant qu'impureté, qui comprend une étape lors de laquelle le trifluorure d'azote est mis en contact avec de l'eau, une étape lors de laquelle le trifluorure d'azote est mis en contact avec une solution basique aqueuse, et une étape lors de laquelle le trifluorure d'azote est mis en contact avec une solution aqueuse d'un agent réducteur. Ce procédé permet d'éliminer les impuretés tout en supprimant la production d'oxydes d'halogène, et le trifluorure d'azote peut être purifié à une grande pureté à faible coût.
PCT/JP2009/067399 2008-10-28 2009-10-06 Procédé et système pour purifier du trifluorure d’azote contenant un halogène ou un composé halogéné en tant qu’impureté WO2010050342A1 (fr)

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JP2008276262A JP2010105825A (ja) 2008-10-28 2008-10-28 ハロゲンまたはハロゲン化合物を不純物として含む三フッ化窒素の精製方法
JP2008-276262 2008-10-28

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108348850A (zh) * 2015-12-01 2018-07-31 昭和电工株式会社 含有氟元素的废气的处理方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0280310A (ja) * 1988-06-01 1990-03-20 Mitsui Toatsu Chem Inc 三弗化窒素ガスの精製方法
JPH03217217A (ja) * 1990-01-19 1991-09-25 Central Glass Co Ltd 三フッ化塩素を含む排ガスの処理方法
JPH11349304A (ja) * 1998-06-05 1999-12-21 Mitsui Chem Inc 高純度三弗化窒素ガスの精製方法
JP2002068716A (ja) * 2000-08-28 2002-03-08 Mitsui Chemicals Inc 高純度ｎｆ３ガスの精製方法
JP2002284512A (ja) * 2001-03-28 2002-10-03 Mitsui Chemicals Inc 高純度三弗化窒素の製造方法
JP2009136709A (ja) * 2007-12-03 2009-06-25 Central Glass Co Ltd ＣｌＯ３Ｆの除去方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0280310A (ja) * 1988-06-01 1990-03-20 Mitsui Toatsu Chem Inc 三弗化窒素ガスの精製方法
JPH03217217A (ja) * 1990-01-19 1991-09-25 Central Glass Co Ltd 三フッ化塩素を含む排ガスの処理方法
JPH11349304A (ja) * 1998-06-05 1999-12-21 Mitsui Chem Inc 高純度三弗化窒素ガスの精製方法
JP2002068716A (ja) * 2000-08-28 2002-03-08 Mitsui Chemicals Inc 高純度ｎｆ３ガスの精製方法
JP2002284512A (ja) * 2001-03-28 2002-10-03 Mitsui Chemicals Inc 高純度三弗化窒素の製造方法
JP2009136709A (ja) * 2007-12-03 2009-06-25 Central Glass Co Ltd ＣｌＯ３Ｆの除去方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108348850A (zh) * 2015-12-01 2018-07-31 昭和电工株式会社 含有氟元素的废气的处理方法
EP3384975A4 (fr) * 2015-12-01 2019-08-07 Showa Denko K.K. Procédé de traitement de gaz d'échappement contenant du fluor élémentaire

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