JPH03296412A - Collection of trifluoromethanesulfonyl fluoride - Google Patents
Collection of trifluoromethanesulfonyl fluorideInfo
- Publication number
- JPH03296412A JPH03296412A JP2099586A JP9958690A JPH03296412A JP H03296412 A JPH03296412 A JP H03296412A JP 2099586 A JP2099586 A JP 2099586A JP 9958690 A JP9958690 A JP 9958690A JP H03296412 A JPH03296412 A JP H03296412A
- Authority
- JP
- Japan
- Prior art keywords
- fluoride
- trifluoromethanesulfonic acid
- gas
- contact
- solvent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SLVAEVYIJHDKRO-UHFFFAOYSA-N trifluoromethanesulfonyl fluoride Chemical compound FC(F)(F)S(F)(=O)=O SLVAEVYIJHDKRO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003682 fluorination reaction Methods 0.000 claims abstract description 10
- 239000011737 fluorine Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- KNWQLFOXPQZGPX-UHFFFAOYSA-N methanesulfonyl fluoride Chemical compound CS(F)(=O)=O KNWQLFOXPQZGPX-UHFFFAOYSA-N 0.000 claims abstract description 5
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract 4
- 239000007789 gas Substances 0.000 claims description 25
- 239000012442 inert solvent Substances 0.000 claims description 10
- 239000010702 perfluoropolyether Substances 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 125000004433 nitrogen atom Chemical group N* 0.000 claims 1
- 125000004430 oxygen atom Chemical group O* 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 9
- 150000003839 salts Chemical class 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 239000012359 Methanesulfonyl chloride Substances 0.000 abstract 1
- WGBZKRKBGGQMSY-UHFFFAOYSA-N fluoromethanesulfonyl fluoride Chemical compound FCS(F)(=O)=O WGBZKRKBGGQMSY-UHFFFAOYSA-N 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- BJBXQQZMELYVMD-UHFFFAOYSA-N 2,2,3,3,4,5,5,6,6-nonafluoromorpholine Chemical compound FN1C(F)(F)C(F)(F)OC(F)(F)C1(F)F BJBXQQZMELYVMD-UHFFFAOYSA-N 0.000 description 1
- DAOUWMXJTNAWNE-UHFFFAOYSA-N C12=C(C(=C(C(=C1F)F)F)F)N(C(C(=C2F)F)(F)F)C(F)(F)F Chemical compound C12=C(C(=C(C(=C1F)F)F)F)N(C(C(=C2F)F)(F)F)C(F)(F)F DAOUWMXJTNAWNE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 alkali metal salt Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- AQZYBQIAUSKCCS-UHFFFAOYSA-N perfluorotripentylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F AQZYBQIAUSKCCS-UHFFFAOYSA-N 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Gas Separation By Absorption (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ペルフルオロアルキルスルホン酸フッ化物、
特にトリフルオロメタンスルホン酸フッ化物の捕集方法
に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides perfluoroalkylsulfonic acid fluorides,
In particular, the present invention relates to a method for collecting trifluoromethanesulfonic acid fluoride.
トリフルオロメタンスルホン酸（ＣＦ、ＳＯ，Ｈ）は、
いわゆる「超強酸」の一種であり、また、耐熱性、耐酸
化還元性に優れているため、近年、有用な酸触媒として
注目されている（たとえば、重合用触媒、異性化触媒）
。また、その酸無水物はアルキル化剤として有用であり
、リチウム塩はリチウム電池電解質として用いられるな
ど、誘導体の工業的利用分野も多岐にわたっている。Trifluoromethanesulfonic acid (CF, SO, H) is
It is a type of so-called "super strong acid" and has excellent heat resistance and redox resistance, so it has recently attracted attention as a useful acid catalyst (e.g., polymerization catalyst, isomerization catalyst).
. In addition, its acid anhydride is useful as an alkylating agent, and its lithium salt is used as a lithium battery electrolyte, and the derivatives are used in a wide variety of industrial fields.
トリフルオロメタンスルホン酸は、工業的には。Trifluoromethanesulfonic acid is industrially available.
以下に示す反応経路に従い製造される：Ｍ（ＯＨ）、、
Ｈ２ＯｃＦ、ｓｏ、Ｍ、、、（２゜ＣＦ、 Ｓ Ｏ，
Ｆ
（ここでＭはアルカリ金属またはアルカリ土類金属を、
ｍは１または２を表わす）
Ｈ，Ｓ Ｏ。Produced according to the reaction route shown below: M(OH),
H2OcF,so,M,,,(2゜CF, SO,
F (where M is an alkali metal or alkaline earth metal,
m represents 1 or 2) H, S O.
ＣＦ、５０３Ｍ ＣＦ、Ｓ○、Ｈ・・・
（３）すなわち、メタンスルホン酸フッ化物またはその
塩化物を電解フッ素化してトリフルオロメタンスルホン
酸フッ化物としく上記（１））、ついで、これをアルカ
リ金属またはアルカリ土類金属水溶液と接触させてトリ
フルオロメタンスルホン酸塩としく上記（２））、得ら
れた塩を硫酸によって加水分解する（上記（３））。CF, 503M CF, S○, H...
(3) That is, methanesulfonic acid fluoride or its chloride is electrolytically fluorinated to form trifluoromethanesulfonic acid fluoride (1)), and then this is brought into contact with an aqueous alkali metal or alkaline earth metal solution to form trifluoride. The resulting salt is hydrolyzed with sulfuric acid ((3)).
しかし、上記電解フツ素化反応においては、生成するト
リフルオロメタンスルホン酸フッ化物が気体（沸点ニー
２３℃）であり、多量の副生成ガス（Ｈ２）で稀釈され
ている。このため、直ちにアルカリ金属またはアルカリ
土類金属水溶液と接触させる方法ではフッ化物の大部分
が溶液中で塩に転化することなく液外に散逸してしまう
。よって、金属塩への転化に先立ってフッ化物のみを効
率的に捕集する必要がある。However, in the electrolytic fluorination reaction, the trifluoromethanesulfonic acid fluoride produced is a gas (boiling point: 23° C.) and diluted with a large amount of by-product gas (H2). For this reason, in a method in which the fluoride is immediately brought into contact with an aqueous alkali metal or alkaline earth metal solution, most of the fluoride is not converted into salt in the solution and is dissipated out of the solution. Therefore, it is necessary to efficiently collect only fluoride prior to conversion into metal salts.
このための捕集方法としては、従来、活性炭等による吸
着法、冷却による液化法、水酸化ナトリウムやアミン等
の塩基を用いた化学吸着法、隔膜を用いた分離捕集法、
溶媒による吸収法等が提案されている。Collection methods for this purpose include conventional adsorption methods using activated carbon, liquefaction methods by cooling, chemisorption methods using bases such as sodium hydroxide and amines, separation and collection methods using diaphragms, etc.
Absorption methods using solvents have been proposed.
しかし、活性炭素による吸着法では、吸着剤単位重量あ
たりの吸着量が十分ではないため、大量のトリフルオロ
メタンスルホン酸フッ化物を吸着させるためには多量の
吸着剤が必要となる。また、脱離工程では通常、熱エネ
ルギーの投入が必要である。液化法では純度の高いトリ
フルオロメタンスルホン酸フッ化物が得られるが、冷却
に要するエネルギーコストが多大であり、加圧液化によ
り冷却温度を上げる場合には多大の設備投資が要求され
る。化学吸着法では、吸着は容易に進行するが、フッ化
物の脱離が困難である。分離捕集法は、電解フツ素化槽
に隔膜を設け、陰極に発生する副生ガスと陽極に発生す
るフッ化物を分離するものであるが、電解槽の構造その
ものを変更しなければならず、既存の設備の設計変更が
必要である。However, in the adsorption method using activated carbon, the amount of adsorption per unit weight of adsorbent is not sufficient, so a large amount of adsorbent is required to adsorb a large amount of trifluoromethanesulfonic acid fluoride. Additionally, the desorption process usually requires the input of thermal energy. Although trifluoromethanesulfonic acid fluoride with high purity can be obtained by the liquefaction method, the energy cost required for cooling is large, and if the cooling temperature is increased by pressurized liquefaction, a large amount of equipment investment is required. In the chemisorption method, adsorption progresses easily, but desorption of fluoride is difficult. In the separation and collection method, a diaphragm is installed in the electrolytic fluorination tank to separate the byproduct gas generated at the cathode from the fluoride generated at the anode, but the structure of the electrolytic tank itself must be changed. , design changes to existing equipment are required.
また、フッ化物ガスを捕集する場合でもこれを直接ＫＯ
Ｈ水溶液に接触させ、該水溶液中に該ガスを吸収させる
と同時に金属塩に転化するという従来法には、 ＫＯＨ
水溶液へのフッ化物の吸収速度が著しく遅く実用性に乏
しいという問題がある。Also, when collecting fluoride gas, it can be directly KOed.
The conventional method of bringing the gas into contact with an aqueous solution of KOH and absorbing the gas into the aqueous solution and simultaneously converting it into a metal salt includes:
There is a problem in that the rate of absorption of fluoride into an aqueous solution is extremely slow and impractical.
本発明者らは、トリフルオロメタンスルホン酸フッ化物
を工業的規模で効率的に捕集する方法を検討した結果、
ある種のフッ素系不活性溶媒がフッ化物吸収力に優れて
おりこれを捕集溶媒として用い、ついで、該溶媒からフ
ッ化物の抽出および金属塩の転化を行なうことで上記課
題が達成できることを見出した。As a result of investigating a method for efficiently collecting trifluoromethanesulfonic acid fluoride on an industrial scale, the present inventors found that
It has been discovered that certain fluorine-based inert solvents have excellent fluoride absorption ability, and that the above-mentioned problems can be achieved by using this as a collection solvent and then extracting the fluoride from the solvent and converting the metal salt. Ta.
本発明は、トリフルオロメタンスルホン酸フッ化物を含
む気体をフッ素系不活性溶媒と接触させることからなる
トリフルオロメタンスルホン酸フッ化物の捕集方法を提
供する。The present invention provides a method for collecting trifluoromethanesulfonic acid fluoride, which comprises contacting a gas containing trifluoromethanesulfonic acid fluoride with a fluorine-based inert solvent.
また、本発明は、特にメタンスルホン酸フッ化物または
メタンスルホン酸塩化物の電解フッ素化により生成した
トリフルオロメタンスルホン酸フッ化物を含む気体混合
物をフッ素系不活性溶媒と接触させることからなるトリ
フルオロメタンスルホン酸フッ化物の捕集方法を提供す
る。In addition, the present invention particularly provides trifluoromethanesulfonate which is produced by contacting a gas mixture containing trifluoromethanesulfonic acid fluoride produced by electrolytic fluorination of methanesulfonic acid fluoride or methanesulfonic acid chloride with a fluorinated inert solvent. A method for collecting acid fluorides is provided.
本発明の方法は、トリフルオロメタンスルホン酸フッ化
物単体またはこれと反応しない任意の気体との混合物に
対して適用できる。特にメタンスルホン酸フッ化物また
はメタンスルホン酸塩化物の電解フッ化により生成した
トリフルオロメタンスルホン酸フッ化物を含む気体混合
物に対して有用である。The method of the present invention can be applied to trifluoromethanesulfonic acid fluoride alone or to a mixture with any gas that does not react with it. It is particularly useful for gas mixtures containing trifluoromethanesulfonic acid fluoride produced by electrolytic fluorination of methanesulfonic acid fluoride or methanesulfonic acid chloride.
本発明で用いるフッ素系不活性溶媒は、本発明の方法が
適用されるトリフルオロメタンスルホン酸フッ化物およ
びこれと混合した気体のいずれとも反応しないものであ
れば、いずれをも用いることができる。炭素、水素、フ
ッ素以外の元素を含有していてもよい。代表的な例とし
ては。As the fluorine-based inert solvent used in the present invention, any solvent can be used as long as it does not react with either the trifluoromethanesulfonic acid fluoride to which the method of the present invention is applied or the gas mixed therewith. It may contain elements other than carbon, hydrogen, and fluorine. A typical example is.
ペルフルオロアルカン
ＣｎＦｘｎ＋ａ （ｎ＝６−２０）
ペルフルオロアルキルアミン
（Ｃ−Ｆｚ ｎ＋□）３Ｎ （ｎ＝３−６）ペルフルオ
ロビシクロアルカン
ペルフルオロモルホリン
（ｒＦｌ−５，ｐｉ−３）
ペルフルオロポリエーテル
ベルフルオロアダマンタン
ベルフルオロシクロエーテル、ペルフルオロビシクロエ
ーテル（ｎ＝ｏ−５，ＦＯ−３Ｊ２−４−３）ペルフル
オロシクロアミン
ペルフルオロビシクロアミン
およびこれらの混合物がある。これらのフッ素系不活性
溶媒は、例えば、２０％にＯＨ水溶液と比べ、フッ化物
の吸収速度が数十倍速い。Perfluoroalkane CnFxn+a (n=6-20) Perfluoroalkylamine (C-Fz n+□) 3N (n=3-6) Perfluorobicycloalkane perfluoromorpholine (rFl-5, pi-3) Perfluoropolyether perfluoroadamantane perfluoro cycloether, perfluorobicycloether (n=o-5, FO-3J2-4-3) perfluorocycloamine perfluorobicycloamine and mixtures thereof. These fluorine-based inert solvents have a fluoride absorption rate several tens of times faster than, for example, a 20% OH aqueous solution.
捕集は、フッ素系不活性溶媒が液体である限り可能であ
るが、好ましくは常圧下、２０℃以下、より好ましくは
一１５℃〜２０℃の温度範囲で行なう。Collection is possible as long as the fluorinated inert solvent is liquid, but is preferably carried out under normal pressure at a temperature of 20°C or less, more preferably in the temperature range of -15°C to 20°C.
２０℃を超え高温になるとトリフルオロメタンスルホン
酸フッ化物およびフッ素系不活性溶媒の逸散量が増え吸
収効率も低下する。また、−１５℃より低温に冷却する
場合には、冷却に要するエネルギーコストが増大し、経
済的に不利である。When the temperature exceeds 20° C., the amount of trifluoromethanesulfonic acid fluoride and the fluorinated inert solvent escaping increases, and the absorption efficiency also decreases. Moreover, when cooling to a temperature lower than -15° C., the energy cost required for cooling increases, which is economically disadvantageous.
トリフルオロメタンスルホン酸フッ化物とフッ素系不活
性溶媒との接触方法は限定されない。The method of contacting the trifluoromethanesulfonic acid fluoride and the fluorinated inert solvent is not limited.
また、本発明の方法により捕集したトリフルオロメタン
スルホン酸フッ化物は、溶媒に含有させたままアルカリ
金属塩に接触させることで、その分離および塩への転化
が容易に達成できる。Moreover, the trifluoromethanesulfonic acid fluoride collected by the method of the present invention can be easily separated and converted into a salt by contacting it with an alkali metal salt while it is contained in a solvent.
実施例１
１Ｑの電解槽を用いて、電流密度ＩＡ／ｄｍ”、電圧５
〜６ｖ、温度８〜１３℃の条件テ、 ＣＨ，Ｓｏ、ＣＲ
を１０．９ｇ／時間ずつ供給しながら連続電解フッ素化
を行なった。Example 1 Using a 1Q electrolytic cell, current density IA/dm", voltage 5
~6V, temperature 8~13℃ conditions, CH, So, CR
Continuous electrolytic fluorination was carried out while supplying 10.9 g/hour of fluorine.
電解フツ素化生成ガスを、始めに水洗塔に導入してＨＦ
、 ＣＱ、を除き、次に内径５ｃ＋ａ、８ Ｘ ８ｍｍ
のラソシヒリングを充填（層高３０ｃｍ） したテフロ
ン製ガス吸収塔に導き、操作温度７〜８℃で、ペルフル
オロ環状エーテル（ＥＦＴＯＰ＠ ＥＦ−ＬｉＯ２：環
状エーテルＣ５Ｆ、 ０ （Ｃ３Ｆ７）と環状エーテル
Ｃ４Ｆ７０ （Ｃ４Ｆ、 ）との混合物）を２７．６ｋ
ｇ／時閉で流しながら、ガスと向流接触させた。The gas produced by electrolytic fluorination is first introduced into a water washing tower and converted into HF.
, except CQ, then inner diameter 5c+a, 8 x 8mm
perfluorocyclic ether (EFTOP@EF-LiO2: cyclic ether C5F,0 (C3F7) and cyclic ether C4F70 (C4F , ) 27.6k
It was brought into countercurrent contact with the gas while flowing at g/hr closed.
吸収塔出入口のガス組成を分析、比較したところＣＦ３
５ｏ２Ｆガスの９７〜９５％が吸収されていた。Analysis and comparison of the gas composition at the entrance and exit of the absorption tower revealed CF3.
97-95% of the 5o2F gas was absorbed.
ペルフルオロ環状エーテルのガスクロマトグラフィー分
析（ｓｉｌｒｃｏｎｅ ＫＦ−９６，１０ｍ、 ３０’
Ｃ）により、相当量のＣＦ、 ５ｏ２Ｆが存在すること
を確認した。Gas chromatography analysis of perfluorocyclic ether (silrcone KF-96, 10m, 30'
C), it was confirmed that a considerable amount of CF and 5o2F were present.
実施例２
実施例１と同様な条件によりＣＨＪＳｏ２Ｃｊｌの電解
フッ素化を行なった。吸収液としてペルフルオロトリブ
チルアミン（ＥＦｒｏｐ＠ ＥＦ−Ｌ１７４ ： （Ｃ
４Ｆ、）、Ｎ）を用いた。Example 2 Electrolytic fluorination of CHJSo2Cjl was performed under the same conditions as in Example 1. Perfluorotributylamine (EFrop@EF-L174: (C
4F, ), N) were used.
吸収管出入口のガス組成を分析、比較したところＣＦ３
５Ｏ□Ｆガスの９５％以上が吸収されていた。Analysis and comparison of the gas composition at the entrance and exit of the absorption tube revealed CF3.
More than 95% of the 5O□F gas was absorbed.
ペルフルオロトリブチルアミンのガスクロマトグラフィ
ー分析により、相当量のＣＦ、 ＳＯ２Ｆの存在を確認
した。Gas chromatography analysis of perfluorotributylamine confirmed the presence of considerable amounts of CF and SO2F.
実施例３
実施例１と同様な電解槽を用いてＣＦ３５ｏ、 Ｆの電
解フッ素化を行なった。ＣＦ３５ｏ□ＦはＣＦ□ｓＯ□
Ｃρと酸性フッ化カリウムＣＫＦ−ＨＦ）水溶液との反
応により合成し、蒸留精製して使用した（ｂρ、１２３
〜１２４℃）。Example 3 Using the same electrolytic cell as in Example 1, electrolytic fluorination of CF35o and F was carried out. CF35o□F is CF□sO□
It was synthesized by the reaction of Cρ with an aqueous solution of acidic potassium fluoride (CKF-HF), purified by distillation, and used (bρ, 123
~124°C).
ＣＦ、 ＳＯ□Ｆを時間当たり９．３ｇずつ供給したほ
がは、実施例１と同様な操作を行なった。The same operation as in Example 1 was carried out in the case where CF and SO□F were supplied at a rate of 9.3 g per hour.
吸収塔呂入口のガス組成を分析により、９５％以上のＣ
Ｆ、 ＳＯ，Ｆが吸収された。ガスの９５％以上が吸収
されていた。またペルフルオロ環状エーテルのガスクロ
マトグラフィー分析から、相当量のＣＦ、 ５０２Ｆの
存在を確認した。Analysis of the gas composition at the inlet of the absorption tower revealed that it contained over 95% C.
F, SO, and F were absorbed. More than 95% of the gas was absorbed. Furthermore, gas chromatography analysis of the perfluorocyclic ether confirmed the presence of considerable amounts of CF and 502F.
実施例４
内径２．１ｃｍ、容積１００１の円筒型容器内を８５％
のＣＦ、 ＳＯ，Ｆガスで満たした（純ガスをａｉｒで
希釈）。次にこの容器に、吸収液としてペルフルオロオ
クタン（Ｃ１Ｆ工、）１５履ｇを加えた。吸収によって
減少していく気体体積をガスビユレットで追跡した。測
定中は系内圧力が大気圧と等しくなるよう調節した。Example 4 85% of the inside of a cylindrical container with an inner diameter of 2.1 cm and a volume of 1001
of CF, SO, and F gas (pure gas diluted with air). Next, 15 g of perfluorooctane (C1F Engineering) was added as an absorption liquid to this container. The gas volume decreasing due to absorption was tracked using a gas billet. During the measurement, the system pressure was adjusted to be equal to atmospheric pressure.
約５０ｍＱ減少するまでに要する時間を測定し、平均の
吸収速度を算出した。吸収実験は、２０℃に空調された
恒温室内で行なった。The time required for the amount to decrease by about 50 mQ was measured, and the average absorption rate was calculated. The absorption experiment was conducted in a constant temperature room air-conditioned at 20°C.
結果を第１表に示す。The results are shown in Table 1.
実施例５
吸収液としてペルフルオロトリペンチルアミン（ＥＦＴ
ＯＰ＠ ＥＦ−Ｌ２１５：（Ｃ，Ｆ□１）３Ｎ）を用い
た以外は実施例４と同様な操作を行ない平均の吸収速度
を求めた。Example 5 Perfluorotripentylamine (EFT) was used as an absorption liquid.
The average absorption rate was determined by performing the same operation as in Example 4 except that OP@EF-L215: (C,F□1)3N) was used.
結果を第１表に示す。The results are shown in Table 1.
実施例６ を求めた。Example 6 I asked for
結果を第１表に示す。The results are shown in Table 1.
実施例７
吸収液としてペルフルオロ−Ｎ−メチルキノリン（Ｃ４
゜Ｆ、、Ｎ）を用いた以外は実施例４と同様な操作を行
ない平均の吸収速度を求めた。Example 7 Perfluoro-N-methylquinoline (C4
The average absorption rate was determined by carrying out the same operation as in Example 4, except for using .degree.F., N).
結果を第１表に示す。The results are shown in Table 1.
比較例１〜５
比較のために１種々のアルカリ水溶液を吸収液として用
いた。Comparative Examples 1 to 5 For comparison, various alkaline aqueous solutions were used as absorption liquids.
結果を第１表に示す。The results are shown in Table 1.
例 実施例４ 実施例５ 実施例６ 実施例７ 比較例１ 比較例２ 比較例３ 比較例４ 比較例５ Ｊｌ」−Ｊし 吸収液 Ｃ，Ｆ工。example Example 4 Example 5 Example 6 Example 7 Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5 Jl”-J absorption liquid C, F engineering.
ＥＦＴＯＰ＠ ＥＦ−Ｌ２１５７
ＫＲＹＴＯＸ■ １４３ＡＡイ
Ｃ工。Ｆ、、Ｎつ
Ｈ，０
２０％−ＮａＯＨ
２０％−ＫＯＨ
４８％−ＫＯＨ
２８％−ＮＨ３
平均吸収速度
（ｔＱ／ｈｒｊｃ＋ｗ２）
約４００以上
吸収が迅速であるため、トリフルオロメタンスルホン酸
フッ化物を連続的に捕集することが可能である。EFTOP@EF-L2157 KRYTOX ■ 143AAi C engineering. F,,N H,0 20%-NaOH 20%-KOH 48%-KOH 28%-NH3 Average absorption rate (tQ/hrjc+w2) Approximately 400 or more Because absorption is rapid, trifluoromethanesulfonic acid fluoride is continuously It is possible to collect
Claims (1)
をフッ素系不活性溶媒と接触させることからなるトリフ
ルオロメタンスルホン酸フッ化物の捕集方法。 ２、請求項第１項に記載の方法であって、該気体がメタ
ンスルホン酸フッ化物またはメタンスルホン酸塩化物の
電解フッ素化により生成したものである方法。 ３、先行するいずれかの請求項に記載の方法であって、
該フッ素系不活性溶媒が、６〜２０個の炭素原子を含む
ペルフルオロアルカン；９〜２０個の炭素原子を含むペ
ルフルオロアルキルアミン；１以上の複素原子を含むも
しくは含まないペルフルオロ単環もしくは縮合環化合物
であって、１〜５個の炭素原子からなる置換基を有しも
しくは有さず該複素原子が窒素原子もしくは酸素原子で
あるもの；およびペルフルオロポリエーテルからなる群
より選ばれるもの、またはその混合物である方法。[Scope of Claims] 1. A method for collecting trifluoromethanesulfonic acid fluoride, which comprises bringing a gas containing trifluoromethanesulfonic acid fluoride into contact with a fluorine-based inert solvent. 2. The method according to claim 1, wherein the gas is produced by electrolytic fluorination of methanesulfonic acid fluoride or methanesulfonic acid chloride. 3. A method according to any preceding claim, comprising:
The fluorinated inert solvent is a perfluoroalkane containing 6 to 20 carbon atoms; a perfluoroalkylamine containing 9 to 20 carbon atoms; a perfluoro monocyclic or fused ring compound containing or not containing one or more heteroatoms; which has or does not have a substituent consisting of 1 to 5 carbon atoms, and the hetero atom is a nitrogen atom or an oxygen atom; and a perfluoropolyether, or a mixture thereof. How to be.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2099586A JP2946103B2 (en) | 1990-04-16 | 1990-04-16 | Method for collecting trifluoromethanesulfonic acid fluoride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2099586A JP2946103B2 (en) | 1990-04-16 | 1990-04-16 | Method for collecting trifluoromethanesulfonic acid fluoride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03296412A true JPH03296412A (en) | 1991-12-27 |
| JP2946103B2 JP2946103B2 (en) | 1999-09-06 |
Family
ID=14251203
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2099586A Expired - Lifetime JP2946103B2 (en) | 1990-04-16 | 1990-04-16 | Method for collecting trifluoromethanesulfonic acid fluoride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2946103B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5575906A (en) * | 1994-07-01 | 1996-11-19 | Haldor Tops.o slashed.e A/S | Process for the electrochemical fluorination of a hydrocarbon substrate |
| WO2001098443A1 (en) * | 2000-06-22 | 2001-12-27 | Extractive | Method for fractionating essential oils using at least a fluorinated solvent |
| JP2007119458A (en) * | 2005-09-30 | 2007-05-17 | Mitsubishi Materials Corp | Potassium perfluoroalkane sulfonate and process for production thereof |
| JP2011046675A (en) * | 2009-08-28 | 2011-03-10 | Mitsubishi Materials Corp | Method and apparatus for recovering perfluoroalkanesulfonyl fluoride |
| WO2012039024A1 (en) * | 2010-09-21 | 2012-03-29 | 三菱マテリアル株式会社 | Method and device for recovering perfluoroalkanesulfonyl fluoride |
-
1990
- 1990-04-16 JP JP2099586A patent/JP2946103B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5575906A (en) * | 1994-07-01 | 1996-11-19 | Haldor Tops.o slashed.e A/S | Process for the electrochemical fluorination of a hydrocarbon substrate |
| WO2001098443A1 (en) * | 2000-06-22 | 2001-12-27 | Extractive | Method for fractionating essential oils using at least a fluorinated solvent |
| FR2810672A1 (en) * | 2000-06-22 | 2001-12-28 | Extractive | Process for the fractionation of essential oils by contact with a fluorinated solvent and separation of fractions from the fluorinated and non-fluorinated phases |
| JP2007119458A (en) * | 2005-09-30 | 2007-05-17 | Mitsubishi Materials Corp | Potassium perfluoroalkane sulfonate and process for production thereof |
| JP2011046675A (en) * | 2009-08-28 | 2011-03-10 | Mitsubishi Materials Corp | Method and apparatus for recovering perfluoroalkanesulfonyl fluoride |
| WO2012039024A1 (en) * | 2010-09-21 | 2012-03-29 | 三菱マテリアル株式会社 | Method and device for recovering perfluoroalkanesulfonyl fluoride |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2946103B2 (en) | 1999-09-06 |
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