JP2010158664A - Detoxifying method of chlorine trifluoride - Google Patents
Detoxifying method of chlorine trifluoride Download PDFInfo
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- JP2010158664A JP2010158664A JP2009252714A JP2009252714A JP2010158664A JP 2010158664 A JP2010158664 A JP 2010158664A JP 2009252714 A JP2009252714 A JP 2009252714A JP 2009252714 A JP2009252714 A JP 2009252714A JP 2010158664 A JP2010158664 A JP 2010158664A
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- 238000000034 method Methods 0.000 title claims abstract description 18
- JOHWNGGYGAVMGU-UHFFFAOYSA-N trifluorochlorine Chemical compound FCl(F)F JOHWNGGYGAVMGU-UHFFFAOYSA-N 0.000 title claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011737 fluorine Substances 0.000 claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 33
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001784 detoxification Methods 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 8
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- XHFXMNZYIKFCPN-UHFFFAOYSA-N perchloryl fluoride Chemical compound FCl(=O)(=O)=O XHFXMNZYIKFCPN-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 59
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004334 fluoridation Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 229910000127 oxygen difluoride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1406—Multiple stage absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/76—Gas phase processes, e.g. by using aerosols
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/10—Oxidants
- B01D2251/108—Halogens or halogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/202—Single element halogens
- B01D2257/2027—Fluorine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/204—Inorganic halogen compounds
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
Description
本発明は、三フッ化塩素及びフッ素から成る混合ガスの除害方法に関する。 The present invention relates to a method for removing a mixed gas composed of chlorine trifluoride and fluorine.
三フッ化塩素（ＣｌＦ3）は下記反応式１に示されるように、塩素とフッ素との直接反
応により合成されることが広く知られている（非特許文献１、２）。
As shown in the following reaction formula 1, chlorine trifluoride (ClF 3 ) is widely known to be synthesized by a direct reaction between chlorine and fluorine (Non-patent Documents 1 and 2).
一般的なＣｌＦ3の製造工程では、反応器で生成したＣｌＦ3は冷却捕集器を通過し、目的の生成物のみが選択的に捕集される。 In a typical ClF 3 of the manufacturing process, ClF 3 produced in the reactor is passed through a cold trap, only the desired product are selectively collected.
通常、冷却捕集器を通過したガス中には未反応のＦ2ガスや捕集しきれなかったＣｌＦ3が含まれているため、水やアルカリ溶液を使用した湿式スクラバー（排ガス処理装置）によって除害処理される。 Normally, the gas that has passed through the cold collector contains unreacted F 2 gas and ClF 3 that could not be collected. Therefore, the wet scrubber (exhaust gas treatment device) using water or an alkali solution was used. Detoxification treatment.
しかしながら、ＣｌＦ3とＦ2の混合ガスを、水を用いた湿式スクラバーで除害処理する場合、下記反応式２に示されるようにフッ素が水と反応することによって、酸素ラジカルが発生する。 However, when the mixed gas of ClF 3 and F 2 is detoxified with a wet scrubber using water, oxygen radicals are generated by the reaction of fluorine with water as shown in the following reaction formula 2.
さらに、下記反応式３に示されるように、発生した酸素ラジカルがＣｌＦ3と反応し、
フッ化ペルクロリル（ＣｌＯ3Ｆ）が発生する。
Furthermore, as shown in the following reaction formula 3, the generated oxygen radical reacts with ClF 3 ,
Perchloryl fluoride (ClO 3 F) is generated.
ＣｌＯ3Ｆは熱的に非常に安定な化合物であり、４７０℃まで加温しないと熱分解しな
い。また、水に不溶で酸やアルカリで分解できない特徴がある。さらに、物性がＣｌＯ3
Ｆと類似したガス中にＣｌＯ3Ｆが低濃度で含まれる場合には、蒸留による分離や濃縮も
難しいため、除去が困難という問題があった。
ClO 3 F is a thermally stable compound and does not thermally decompose unless heated to 470 ° C. In addition, it is insoluble in water and cannot be decomposed with acid or alkali. Furthermore, the physical properties are ClO 3
When ClO 3 F is contained at a low concentration in a gas similar to F, there is a problem that separation and concentration by distillation are difficult and removal is difficult.
上記問題の対策において、フッ素含有ガスからフッ素ガスあるいは酸素フッ化物を除去する方法として、硫黄系還元剤と塩基性化合物を含む吸収液を使用する方法が提案されている（特許文献１）。 As a countermeasure for the above problem, as a method for removing fluorine gas or oxygen fluoride from a fluorine-containing gas, a method using an absorbing solution containing a sulfur-based reducing agent and a basic compound has been proposed (Patent Document 1).
しかしながら、特許文献１に提案されている硫黄系還元剤と塩基性化合物を含む吸収液を使用する方法では、還元剤自体の価格が高価であり、さらに、吸収液中の還元剤の濃度管理が必要となるため、湿式スクラバーを用いた除害処理工程の操作が煩雑となる問題点があった。 However, in the method using an absorbing solution containing a sulfur-based reducing agent and a basic compound proposed in Patent Document 1, the price of the reducing agent itself is expensive, and furthermore, the concentration control of the reducing agent in the absorbing solution is possible. Therefore, there is a problem that the operation of the detoxification process using the wet scrubber becomes complicated.
そこで、本発明は、ＣｌＦ3とＦ2を含む混合ガスを湿式スクラバーによって除害処理する際、難分解性物質のＣｌＯ3Ｆの発生を抑制することができる除害方法を提供すること
を課題とする。
Accordingly, the present invention provides a detoxification method that can suppress the generation of ClO 3 F, a hardly decomposable substance, when detoxifying a mixed gas containing ClF 3 and F 2 with a wet scrubber. And
本発明者等は、上記課題を解決するために、鋭意検討した結果、ＣｌＦ3とＦ2を含む混合ガスを湿式スクラバーによって除害処理する前段階において、加熱反応部を設け、下記反応式４に示されるように、混合ガスにハロゲンガスを添加することによって未反応のフッ素ガスをハロゲンガスと反応させ、未反応のフッ素ガスを大幅に低減させ、従来の湿式スクラバーを用いるＣｌＦ3の除害方法において問題となっていた難分解性物質のＣｌＯ3Ｆの発生を抑制することが可能であることを見出し、本発明に至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have provided a heating reaction section in a stage prior to the detoxification treatment of the mixed gas containing ClF 3 and F 2 with a wet scrubber, and the following reaction formula 4 As shown in FIG. 4, by adding halogen gas to the mixed gas, unreacted fluorine gas is reacted with halogen gas, greatly reducing unreacted fluorine gas, and detoxification of ClF 3 using a conventional wet scrubber The inventors have found that it is possible to suppress the generation of ClO 3 F, which is a hardly decomposable substance, which has been a problem in the method, and have reached the present invention.
すなわち、本発明は、三フッ化塩素及びフッ素から成る混合ガスを、湿式スクラバーによって除害処理する方法であって、湿式スクラバーによる除害処理の前段階において、前記混合ガスに、ハロゲンガスＸ2（Ｘ＝Ｃｌ、Ｂｒ又はＩを示す。）を添加し、前記混合
ガス中のフッ素とハロゲンガスＸ2（Ｘ＝Ｃｌ、Ｂｒ又はＩを示す。）を反応させること
によって、前記混合ガス中のフッ素を低減し、湿式スクラバーで生成するフッ化ペルクロリルの生成を未然に防止することを特徴とする除害方法を提供する。
That is, the present invention is a method of detoxifying a mixed gas composed of chlorine trifluoride and fluorine with a wet scrubber, and in the pre-stage of the detoxifying process with a wet scrubber, the mixed gas contains a halogen gas X 2. (Indicating X = Cl, Br or I) and reacting fluorine in the mixed gas with a halogen gas X 2 (indicating X = Cl, Br or I) in the mixed gas. There is provided a detoxification method characterized by reducing fluorine and preventing the formation of perchloryl fluoride generated by a wet scrubber.
本発明は、ＣｌＦ3とＦ2を含む混合ガスを湿式スクラバーによって除害処理する際に、難分解性物質のＣｌＯ3Ｆの発生を大幅に抑制することが可能であり、難分解性物質のＣ
ｌＯ3Ｆの処理に使用されていた高価な還元剤の使用や煩雑な濃度管理を行う必要がない
簡便な方法を提供することが可能となる。
In the present invention, when a mixed gas containing ClF 3 and F 2 is detoxified by a wet scrubber, generation of ClO 3 F as a hardly decomposable substance can be greatly suppressed. C
It is possible to provide a simple method that does not require the use of an expensive reducing agent used for the treatment of lO 3 F or complicated concentration control.
さらに、本発明は、湿式スクラバーによる除害処理の前段階において、大幅に未反応のフッ素ガスを低減させることができるため、湿式スクラバーにおいて毒性の高い二フッ化酸素（ＯＦ2）などのフッ化酸素化合物の発生を抑制することにも効果を奏する。 Furthermore, the present invention can significantly reduce unreacted fluorine gas in the pre-stage of the detoxification treatment with the wet scrubber, so that fluoridation such as oxygen difluoride (OF 2 ) which is highly toxic in the wet scrubber. It is also effective in suppressing the generation of oxygen compounds.
以下、本発明の好ましい実施態様の一例を説明する。 Hereinafter, an example of a preferred embodiment of the present invention will be described.
処理対象となる三フッ化塩素とフッ素の混合ガスには、ＣｌＦ5、ＣｌＦ、ＢｒＦ5、ＢｒＦ3、ＢｒＦ、ＩＦ7、ＩＦ5、ＩＦ3、ＩＦ、ＮＦ3等の他のインターハロゲンガスが含
まれることを妨げない。
Other interhalogen gases such as ClF 5 , ClF, BrF 5 , BrF 3 , BrF, IF 7 , IF 5 , IF 3 , IF, NF 3 are included in the mixed gas of chlorine trifluoride and fluorine to be treated. Does not prevent it from being included.
未反応のフッ素ガスを低減するための原料ガスにはフッ素以外のハロゲンガスが用いられ、塩素、臭素、又はヨウ素を使用することができる。 A halogen gas other than fluorine is used as a raw material gas for reducing unreacted fluorine gas, and chlorine, bromine, or iodine can be used.
加えるフッ素以外のハロゲンガスは、未反応のフッ素ガスに対して、１．０当量以上加えることが好ましい。 The halogen gas other than fluorine to be added is preferably added in an amount of 1.0 equivalent or more with respect to the unreacted fluorine gas.
また、加えるフッ素以外のハロゲンガスは、特に、希釈せずに使用することがきるが、窒素やアルゴンなどの不活性ガスによって希釈して使用することもできる。 Further, the halogen gas other than fluorine to be added can be used without being diluted, but it can be diluted with an inert gas such as nitrogen or argon.
反応器に用いる材質は、高温でのフッ素ガス耐性が高く、かつ、充分な機械的強度を有するニッケルまたはモネルを使用することが好ましい。 The material used for the reactor is preferably nickel or monel which has high resistance to fluorine gas at high temperatures and has sufficient mechanical strength.
反応温度は反応部の温度が２００℃〜４００℃であることが好ましく、特に、好ましくは３００℃〜３５０℃が好適である。２００℃より低い温度では反応が進行しにくく、４００℃より高い温度では、反応器を著しく腐食する可能性があるため好ましくない。 The reaction temperature is preferably 200 ° C to 400 ° C, particularly preferably 300 ° C to 350 ° C. The reaction is difficult to proceed at a temperature lower than 200 ° C., and a temperature higher than 400 ° C. is not preferable because the reactor may be significantly corroded.
フッ素濃度が１〜１０％の混合ガス中のフッ素を１〜１０ｐｐｍ程度に低減させるには、反応器に導入した混合ガスを少なくとも３０秒以上滞留させることが好ましい。 In order to reduce the fluorine in the mixed gas having a fluorine concentration of 1 to 10% to about 1 to 10 ppm, it is preferable to retain the mixed gas introduced into the reactor for at least 30 seconds or more.
反応器に導入する三フッ化塩素及びフッ素から成る混合ガスおよびハロゲンガスの供給方法は、反応器に供給可能であれば特に限定されない。 There are no particular limitations on the method of supplying the mixed gas and halogen gas comprising chlorine trifluoride and fluorine introduced into the reactor as long as they can be supplied to the reactor.
除害処理に用いる湿式スクラバーは、水又はアルカリ溶液を用いたスクラバーを使用することが好ましく、特に、１段目に水スクラバー、２段目にアルカリスクラバーを使用することが好ましい。 As the wet scrubber used for the detoxification treatment, it is preferable to use a scrubber using water or an alkaline solution, and it is particularly preferable to use a water scrubber in the first stage and an alkali scrubber in the second stage.
また、湿式スクラバーに使用するアルカリ溶液としては、ＫＯＨ溶液、ＮａＯＨ溶液、などを用いることができるが、特に、水に対する溶解度が比較的高いＫＯＨ溶液を用いることが好ましい。 In addition, as the alkaline solution used for the wet scrubber, a KOH solution, a NaOH solution, or the like can be used. In particular, it is preferable to use a KOH solution having a relatively high solubility in water.
以下の実施例により、本発明を説明するが、本発明はこれらの実施例に限定されるものではない。 The following examples illustrate the invention, but the invention is not limited to these examples.
図１に、本発明を用いた実験の概略系統図を示す。マスフローコントローラー１、２によって、個々にハロゲンガスおよび三フッ化塩素ガスとフッ素ガスの混合ガスの流量を制御し、ニッケル製筒型反応器３にガスを導入する。ニッケル製筒型反応器３は、外部に設置されているヒーター４によって所定温度に加熱することができる。 FIG. 1 shows a schematic system diagram of an experiment using the present invention. The mass flow controllers 1 and 2 individually control the flow rates of the halogen gas, the mixed gas of chlorine trifluoride gas and fluorine gas, and introduce the gas into the nickel tubular reactor 3. The nickel cylindrical reactor 3 can be heated to a predetermined temperature by a heater 4 installed outside.
あらかじめ所定温度に加熱されたニッケル製筒型反応器３に導入されたガスを所定時間反応させた後、ニッケル製筒型反応器３の後段に連結された水とＫＯＨ濃度が０．１ｍｏｌ/ｌのアルカリ溶液のスクラバー（排ガス処理装置）５、６によって除害処理操作を行
う。
After the gas introduced into the nickel cylindrical reactor 3 heated to a predetermined temperature in advance is reacted for a predetermined time, the water and KOH concentration connected to the subsequent stage of the nickel cylindrical reactor 3 are 0.1 mol / l. The scrubber (exhaust gas treatment device) 5 and 6 of the alkaline solution is used for the detoxification treatment.
さらに、スクラバー流通の出口ガスをサンプリングし、ＦＴ−ＩＲ（大塚電子社製 ＩＧ−１０００）で分析し、ＣｌＯ3Ｆの濃度を測定する。
［実施例１］
内径３０ｍｍ、長さ６００ｍｍのニッケル製筒型反応器３の外壁温度を３５０℃に設定し、マスフローコントローラー１を用いて、２．８ｍｏｌ％のフッ素ガスと３．５ｍｏｌ％のＣｌＦ3の混合ガスを７５ｍｌ/ｍｉｎ、マスフローコントローラー２を用いて、３
．４ｍｏｌ％の塩素ガスを１０ｍｌ/ｍｉｎの流量で、ニッケル製筒型反応器３に導入し
、３０秒反応させたあと、後段に連結された水とＫＯＨ濃度が０．１ｍｏｌ/ｌのアルカ
リ溶液のスクラバー（排ガス処理装置）５、６によって除害処理した後、スクラバー流通の出口ガスをサンプリングし、ＦＴ−ＩＲ（大塚電子社製 ＩＧ−１０００）を用いてＣｌＯ3Ｆ濃度を分析したところ、１８０ｖｏｌｐｐｍであった。
［比較例１］
塩素ガスを添加しない以外は、実施例１と同条件で行った。その結果、サンプリングしたガス中のＣｌＯ3Ｆ濃度は６０００ｖｏｌｐｐｍであった。
［実施例２］
内径１２．４ｍｍ、長さ１０００ｍｍのニッケル製筒型反応器３の外壁温度を３５０℃に設定し、マスフローコントローラー１を用いて、５．０ｍｏｌ％のフッ素ガスと３．０ｍｏｌ％のＣｌＦ3の混合ガスを４９３ｍｌ/ｍｉｎ、マスフローコントローラー２を用
いて、６．０ｍｏｌ％の塩素ガスを４４ｍｌ/ｍｉｎの流量で、ニッケル製筒型反応器３
に導入し、３０秒反応させたあと、後段に連結された水とＫＯＨ濃度が０．１ｍｏｌ/ｌ
のアルカリ溶液のスクラバー（排ガス処理装置）５、６によって除害処理した後、スクラバー流通の出口ガスをサンプリングし、ＦＴ−ＩＲ（大塚電子社製 ＩＧ−１０００）を用いてＣｌＯ3Ｆ濃度を分析したところ、４ｖｏｌｐｐｍであった。
［比較例２］
塩素ガスを添加しない以外は、実施例２と同条件で行った。その結果、サンプリングしたガス中のＣｌＯ3Ｆ濃度は３５００ｖｏｌｐｐｍであった。
［実施例３］
内径３０ｍｍ、長さ６００ｍｍのニッケル製筒型反応器３の外壁温度を３７０℃に設定し、マスフローコントローラー１を用いて、２．８ｍｏｌ％のフッ素ガスと３．５ｍｏｌ％のＣｌＦ３の混合ガスを７５ｍｌ/ｍｉｎ、マスフローコントローラー２を用いて、３．４ｍｏｌ％の塩素ガスを１０ｍｌ/ｍｉｎの流量で、ニッケル製筒型反応器３に導入し、３０秒反応させたあと、後段に連結された水とＫＯＨ濃度が０．１ｍｏｌ/ｌのアルカリ溶液のスクラバー（排ガス処理装置）５、６によって除害処理した後、スクラバー流通の出口ガスをサンプリングし、ＦＴ−ＩＲ（大塚電子社製 ＩＧ−１０００）を用いてＣｌＯ3Ｆ濃度を分析したところ、１６０ｖｏｌｐｐｍであった。
［比較例３］
塩素ガスを添加しない以外は、実施例３と同条件で行った。その結果、サンプリングしたガス中のＣｌＯ3Ｆ濃度は５６００ｖｏｌｐｐｍであった。
Further, the outlet gas of the scrubber circulation is sampled and analyzed by FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.), and the concentration of ClO 3 F is measured.
[Example 1]
The outer wall temperature of the nickel cylindrical reactor 3 having an inner diameter of 30 mm and a length of 600 mm was set to 350 ° C., and a mass flow controller 1 was used to mix a mixed gas of 2.8 mol% fluorine gas and 3.5 mol% ClF 3. 75 ml / min, 3 using mass flow controller 2
. After introducing 4 mol% chlorine gas into the nickel cylindrical reactor 3 at a flow rate of 10 ml / min and reacting for 30 seconds, water connected to the latter stage and an alkaline solution having a KOH concentration of 0.1 mol / l After detoxification with scrubbers (exhaust gas treatment devices) 5 and 6, the outlet gas of scrubber circulation was sampled and analyzed for ClO 3 F concentration using FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.). Met.
[Comparative Example 1]
The test was performed under the same conditions as in Example 1 except that no chlorine gas was added. As a result, the ClO 3 F concentration in the sampled gas was 6000 volppm.
[Example 2]
The outer wall temperature of the nickel cylindrical reactor 3 having an inner diameter of 12.4 mm and a length of 1000 mm is set to 350 ° C., and the mass flow controller 1 is used to mix 5.0 mol% fluorine gas and 3.0 mol% ClF 3 . Using a gas flow of 493 ml / min and mass flow controller 2, 6.0 mol% chlorine gas at a flow rate of 44 ml / min, nickel tubular reactor 3
After the reaction for 30 seconds, the water and KOH concentration connected in the latter stage are 0.1 mol / l.
After scrubbing with an alkali solution scrubber (exhaust gas treatment device) 5 and 6, the outlet gas of scrubber circulation was sampled and analyzed for ClO 3 F concentration using FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) As a result, it was 4 volppm.
[Comparative Example 2]
It carried out on the same conditions as Example 2 except not adding chlorine gas. As a result, the ClO 3 F concentration in the sampled gas was 3500 vol ppm.
[Example 3]
The outer wall temperature of the nickel tubular reactor 3 having an inner diameter of 30 mm and a length of 600 mm was set to 370 ° C., and a mass flow controller 1 was used to mix a mixed gas of 2.8 mol% fluorine gas and 3.5 mol% ClF 3. Using a mass flow controller 2 at 75 ml / min, 3.4 mol% chlorine gas was introduced into the nickel tubular reactor 3 at a flow rate of 10 ml / min, reacted for 30 seconds, and then water connected to the subsequent stage. And KOH concentration of 0.1 mol / l alkaline solution scrubber (exhaust gas treatment device) 5 and 6, sampling the scrubber distribution outlet gas, FT-IR (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) Was used to analyze the ClO 3 F concentration and found to be 160 volppm.
[Comparative Example 3]
It carried out on the same conditions as Example 3 except not adding chlorine gas. As a result, the ClO 3 F concentration in the sampled gas was 5600 volppm.
１、２：マスフローコントローラー
３：反応器
４：ヒーター
５：水スクラバー
６：アルカリスクラバー
７：サンプリング箇所
1, 2: Mass flow controller 3: Reactor 4: Heater 5: Water scrubber 6: Alkaline scrubber 7: Sampling location
Claims (3)
湿式スクラバーによる除害処理の前段階において、前記混合ガスに、ハロゲンガスＸ2（
Ｘ＝Ｃｌ、Ｂｒ又はＩを示す。）を添加し、前記混合ガス中のフッ素とハロゲンガスＸ2
（Ｘ＝Ｃｌ、Ｂｒ又はＩを示す。）を反応させることによって、前記混合ガス中のフッ素を低減し、湿式スクラバーで生成するフッ化ペルクロリル（ＣｌＯ3Ｆ）の生成を未然に
防止することを特徴とする除害方法。 A method of detoxifying a mixed gas comprising at least chlorine trifluoride and fluorine with a wet scrubber,
In the previous stage of the detoxification treatment with the wet scrubber, the mixed gas is added with halogen gas X 2 (
X = Cl, Br or I is shown. ), And fluorine and halogen gas X 2 in the mixed gas
(Representing X = Cl, Br, or I) to reduce fluorine in the mixed gas and to prevent the formation of perchloryl fluoride (ClO 3 F) generated by a wet scrubber. Characteristic abatement method.
ｒ又はＩを示す。）を添加することを特徴とする請求項１に記載の方法。 1.0 equivalent or more of halogen gas X 2 (X = Cl or B relative to fluorine gas in the mixed gas)
r or I is shown. ) Is added. The method according to claim 1.
℃〜４００℃の温度範囲で反応させることを特徴とする請求項１又は請求項２に記載の方法。 Fluorine and halogen gas X 2 (X = Cl, Br or I is shown) in the mixed gas is 200.
The method according to claim 1 or 2, wherein the reaction is performed in a temperature range of from ° C to 400 ° C.
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| KR1020117008395A KR101343961B1 (en) | 2008-12-11 | 2009-11-09 | Method for eliminating unwanted substances from a mixed gas comprising chlorine trifluoride and fluorine |
| PCT/JP2009/069027 WO2010067677A1 (en) | 2008-12-11 | 2009-11-09 | Method for eliminating unwanted substances from chlorine trifluoride |
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| CN104555927B (en) * | 2014-12-31 | 2016-07-20 | 中国船舶重工集团公司第七一八研究所 | A kind of purification process of chlorine trifluoride |
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| JPH11128676A (en) * | 1997-10-31 | 1999-05-18 | Japan Pionics Co Ltd | Purification of harmful gas |
| JP2000093745A (en) * | 1998-09-22 | 2000-04-04 | Kashiyama Kogyo Kk | Waste gas treatment method and treatment apparatus |
| JP2004351364A (en) * | 2003-05-30 | 2004-12-16 | Ebara Corp | Method, agent and apparatus for treating exhaust gas containing halogenated inorganic gas containing chlorine trifluoride |
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| JP2000093745A (en) * | 1998-09-22 | 2000-04-04 | Kashiyama Kogyo Kk | Waste gas treatment method and treatment apparatus |
| JP2004351364A (en) * | 2003-05-30 | 2004-12-16 | Ebara Corp | Method, agent and apparatus for treating exhaust gas containing halogenated inorganic gas containing chlorine trifluoride |
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