JPH0920765A - Separation of hexafluoropropylene oxide and hexafluoropropylene - Google Patents
Separation of hexafluoropropylene oxide and hexafluoropropyleneInfo
- Publication number
- JPH0920765A JPH0920765A JP17376295A JP17376295A JPH0920765A JP H0920765 A JPH0920765 A JP H0920765A JP 17376295 A JP17376295 A JP 17376295A JP 17376295 A JP17376295 A JP 17376295A JP H0920765 A JPH0920765 A JP H0920765A
- Authority
- JP
- Japan
- Prior art keywords
- hexafluoropropylene
- hfp
- hydrogen
- hfpo
- halogenated hydrocarbon
- 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
Landscapes
- Epoxy Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、本質的にヘキサフ
ルオロプロピレンオキシド（以下、ＨＦＰＯと記す。）
とヘキサフルオロプロピレン（以下、ＨＦＰと記す）か
らなる混合物から高純度のＨＦＰＯを分離する方法に関
する。また、本発明は、ＨＦＰを分離する方法に関す
る。TECHNICAL FIELD The present invention essentially relates to hexafluoropropylene oxide (hereinafter referred to as HFPO).
The present invention relates to a method for separating high-purity HFPO from a mixture consisting of and hexafluoropropylene (hereinafter referred to as HFP). The invention also relates to a method of separating HFP.
【０００２】[0002]
【従来の技術】ＨＦＰＯは、各種フッ素化合物、たとえ
ばフッ素系樹脂やエラストマーの中間体であるヘキサフ
ルオロアセトン、パーフルオロアルキルビニルエーテル
などの原料として重要な化合物である。またそのオリゴ
マーは潤滑油や熱媒油等に、広く使用されている。2. Description of the Related Art HFPO is an important compound as a raw material for various fluorine compounds such as hexafluoroacetone and perfluoroalkyl vinyl ether, which are intermediates of fluorine resins and elastomers. Further, the oligomer is widely used as a lubricating oil, a heat transfer oil and the like.
【０００３】ＨＦＰＯの製造法としては、従来より種々
の方法が知られており、一般には、ＨＦＰを酸化して製
造する方法が用いられている。酸化方法としては、分子
状酸素、次亜塩素酸塩、有機過酸化物などの酸化剤を使
用する方法や、電解酸化法等が知られている。As a method for producing HFPO, various methods have hitherto been known, and a method for producing HFP by oxidation is generally used. As an oxidation method, a method using an oxidizing agent such as molecular oxygen, hypochlorite, or an organic peroxide, or an electrolytic oxidation method is known.
【０００４】しかし、従来の酸化方法では、いずれの方
法においても未反応のＨＦＰが残存する問題があり、生
成物はＨＦＰＯとＨＦＰの混合物として得られる。した
がって、高純度のＨＦＰＯを得るには、該混合物からＨ
ＦＰＯを分離することが必要である。また、ＨＦＰＯを
効率良く製造するためには、未反応のＨＦＰを再利用す
るために分離回収して酸化工程へ再循環することが必要
である。However, in any of the conventional oxidation methods, there is a problem that unreacted HFP remains, and the product is obtained as a mixture of HFPO and HFP. Therefore, in order to obtain high-purity HFPO, H 2
It is necessary to separate the FPO. Further, in order to efficiently produce HFPO, it is necessary to separate and collect unreacted HFP for recycling and recycle it to the oxidation step.
【０００５】しかしＨＦＰＯとＨＦＰの各々を蒸留分離
しようとする場合、ＨＦＰとＨＦＰＯの沸点は、それぞ
れ、−２９．４℃と−２７．４℃と近接しているために
蒸留分離は困難である問題がある。また、混合物中に存
在するＨＦＰに臭素を付加して二臭化物とし、これを蒸
留分離することも試みられたが、この方法では、未反応
ＨＦＰの再利用はできない問題がある。However, when trying to separate each of HFPO and HFP by distillation, it is difficult to separate them by distillation because the boiling points of HFP and HFPO are close to −29.4 ° C. and −27.4 ° C., respectively. There's a problem. Attempts have also been made to add bromine to HFP existing in the mixture to form a dibromide, which is then separated by distillation, but this method has a problem that unreacted HFP cannot be reused.
【０００６】[0006]
【発明が解決しようとする課題】そこで、上記の問題を
解決する方法として、本質的にＨＦＰとＨＦＰＯからな
る混合物を抽出蒸留により分離する方法が提案されてい
る。Therefore, as a method for solving the above problems, a method of separating a mixture essentially consisting of HFP and HFPO by extractive distillation has been proposed.
【０００７】抽出蒸留の抽出媒体としては、特公昭４２
−１４９３３に、置換基が炭素数１〜４のアルキル基ま
たはアルコキシ基である１〜３置換のベンゼン化合物、
エーテルのアルキル基が炭素数１〜２個であるエチレン
グリコールまたはジエチレングリコールのジアルキルエ
ーテル、アルキル基の炭素数が１〜４のジアルキルカー
ボネート、四塩化炭素、クロロホルムが提案されてい
る。As an extraction medium for extractive distillation, Japanese Patent Publication No.
-14933, a 1-3-substituted benzene compound in which the substituent is an alkyl group or an alkoxy group having 1 to 4 carbon atoms,
Proposed are ethylene glycol or diethylene glycol dialkyl ethers having an alkyl group of 1 to 2 carbon atoms, dialkyl carbonates having an alkyl group of 1 to 4 carbon atoms, carbon tetrachloride, and chloroform.
【０００８】また、特開昭５３−２１１０９には、２個
以上の炭素原子を含む塩素化炭化水素、または１個以上
のアルキル基（３個以上の炭素を含み、分岐している）
を含むジアルキルエーテルが、特公昭５４−２９４８５
には１，２−ジクロロエタンが、特開昭５７−１５８７
７３には塩化メチレンが、提案されている。Further, JP-A-53-21109 discloses a chlorinated hydrocarbon containing two or more carbon atoms, or one or more alkyl groups (containing three or more carbons and branched).
Dialkyl ethers containing
1,2-dichloroethane is disclosed in JP-A-57-1587.
Methylene chloride is proposed for 73.
【０００９】しかしこれらの抽出媒体は、可燃性物質
（ジメトキエタン、トルエン、ジアルキルエーテル、
１，２−ジクロロエタン等）であったり、オゾン層保護
法に基づく規制物質（四塩化炭素等）として１９９６年
以降使用できなくなる物質であるという問題がある。ま
た、塩化メチレン、クロロホルム等は、抽出媒体として
リサイクル使用ができるほど安定性が高くない問題があ
る。However, these extraction media are combustible substances (dimethoethane, toluene, dialkyl ether,
There is a problem that it is a substance that cannot be used after 1996 as a regulated substance (carbon tetrachloride and the like) based on the ozone layer protection law, such as 1,2-dichloroethane). Further, methylene chloride, chloroform and the like have a problem that they are not so stable that they can be recycled and used as extraction media.
【００１０】本発明者は、抽出蒸留によって高純度のＨ
ＦＰＯとＨＦＰを得るための抽出媒体として、以下の
（１）〜（８）の条件について検討した。The inventor of the present invention has found that high-purity H
The following conditions (1) to (8) were examined as the extraction medium for obtaining FPO and HFP.
【００１１】（１）抽出媒体として充分な相対揮発度を
有する物質であること。 （２）ＨＦＰ、ＨＦＰＯと共沸混合物を形成しない物質
であること。 （３）環境への影響が小さく、特にオゾン層破壊を起こ
す可能性が低い物質であること。 （４）抽出媒体がＨＦＰ、ＨＦＰＯと反応しにく、安定
剤を必要としないこと。 （５）加熱・冷却を含む条件下で、液体として存在し、
リサイクル使用に耐えられる安定性を有すること。 （６）安価であり、入手が容易なこと。 （７）人体への安全性が確認されていること。 （８）不燃性である（または、引火点をもたない）こ
と。(1) A substance having a sufficient relative volatility as an extraction medium. (2) A substance that does not form an azeotropic mixture with HFP and HFPO. (3) A substance that has a small impact on the environment and is particularly unlikely to cause ozone layer depletion. (4) The extraction medium does not easily react with HFP and HFPO and does not require a stabilizer. (5) Exists as a liquid under conditions including heating and cooling,
It must be stable enough to be recycled. (6) It is inexpensive and easily available. (7) The safety to the human body has been confirmed. (8) Be nonflammable (or have no flash point).
【００１２】すなわち、本発明の目的は、抽出媒体とし
て安価に入手でき、従来の抽出媒体と同等の分離効果を
有するという経済的な条件だけでなく、使用条件下で安
定かつ難燃性であり、かつ、環境に対しての影響が小さ
く、人体に対しても安全であるという経済的・実用的な
条件および環境上の条件において優れた抽出媒体を探索
・選定することにある。That is, the object of the present invention is not only economical conditions that it can be obtained as an extraction medium at a low price and has a separation effect equivalent to that of a conventional extraction medium, but that it is stable and flame-retardant under use conditions. In addition, it is to search and select an extraction medium that is excellent in economic and practical conditions that are small in environmental impact and safe for the human body and environmental conditions.
【００１３】[0013]
【課題を解決するための手段】本発明は、本質的にヘキ
サフルオロプロピレンオキシドとヘキサフルオロプロピ
レンからなる混合物に、一般式（１）で表される含水素
ハロゲン化炭化水素の少なくとも１種を接触させて、ヘ
キサフルオロプロピレンオキシドを分離回収し、つぎに
ヘキサフルオロプロピレンを含む含水素ハロゲン化炭化
水素を加熱してヘキサフルオロプロピレンを発生させ回
収することを特徴とする、ヘキサフルオロプロピレンオ
キシドとヘキサフルオロプロピレンの分離方法である。According to the present invention, a mixture consisting essentially of hexafluoropropylene oxide and hexafluoropropylene is contacted with at least one hydrogen-containing halogenated hydrocarbon represented by the general formula (1). Hexafluoropropylene oxide is separated and recovered, and then the hydrogen-containing halogenated hydrocarbon containing hexafluoropropylene is heated to generate and recover hexafluoropropylene. It is a method of separating propylene.
【００１４】[0014]
【化３】Ｃn Ｈa Ｃｌb Ｆc （１）Embedded image C n H a Cl b F c (1)
【００１５】ただし、式（１）において、ｎは２〜６の
整数、ａは１≦ａ≦ｎ＋１を満たす整数、ｂは１≦ｂ≦
２ｎを満たす整数、ｃは１≦ｃ≦２ｎを満たす整数であ
り、ａ＋ｂ＋ｃ＝２ｎ＋２である。However, in the formula (1), n is an integer of 2 to 6, a is an integer satisfying 1 ≦ a ≦ n + 1, and b is 1 ≦ b ≦.
An integer satisfying 2n, c is an integer satisfying 1 ≦ c ≦ 2n, and a + b + c = 2n + 2.
【００１６】以下、本発明を詳細に説明する。本質的に
ＨＦＰＯとＨＦＰからなる混合物の入手経路について
は、特に限定されない。通常の場合は、ＨＦＰを、分子
状酸素、次亜塩素酸塩、有機過酸化物などの酸化剤によ
って酸化して、または、電解酸化法によって酸化してＨ
ＦＰＯを製造する際の生成物が挙げられる。Hereinafter, the present invention will be described in detail. The acquisition route of the mixture consisting essentially of HFPO and HFP is not particularly limited. In the usual case, HFP is oxidized by molecular oxygen, hypochlorite, an organic peroxide, or other oxidizing agent, or by an electrolytic oxidation method to produce H
The products in the production of FPO are mentioned.
【００１７】該混合物におけるＨＦＰＯとＨＦＰの割合
についても、特に限定されず、いずれの割合であっても
よい。たとえば、ＨＦＰを酸化してＨＦＰＯを製造する
際の生成物を用いる場合の割合は、ＨＦＰＯの１重量部
に対しＨＦＰの０．１〜１０重量部程度である。本質的
にＨＦＰＯとＨＦＰからなる混合物は、ＨＦＰＯおよび
ＨＦＰのみからなるのが好ましいが、少量の他の化合物
を含んでいてもよい。The ratio of HFPO and HFP in the mixture is not particularly limited and may be any ratio. For example, the ratio of the product used in the production of HFPO by oxidizing HFP is about 0.1 to 10 parts by weight of HFP per 1 part by weight of HFPO. The mixture consisting essentially of HFPO and HFP preferably consists only of HFPO and HFP, but may contain minor amounts of other compounds.
【００１８】本発明においては、本質的にＨＦＰＯとＨ
ＦＰからなる混合物に、一般式（１）で表される含水素
ハロゲン化炭化水素（以下、含水素ハロゲン化炭化水素
（１）と記す。）の少なくとも１種を接触させる。In the present invention, essentially HFPO and H
At least one hydrogen-containing halogenated hydrocarbon represented by the general formula (1) (hereinafter, referred to as hydrogen-containing halogenated hydrocarbon (1)) is contacted with the mixture of FP.
【００１９】本発明の、含水素ハロゲン化炭化水素
（１）は、実用性に優れた抽出媒体である。すなわち、
含水素ハロゲン化炭化水素（１）は、分子中に１個以上
の水素原子を含む構造を有することから、１９９６年以
降に使用が規制される特定フロン等には含まれない化合
物である。また、オゾン層破壊を起こす可能性が低いた
め、環境への影響が小さい化合物であり、分子中の水素
数が炭素数＋１以下であることから、不燃性または燃焼
範囲を有していても引火点をもたない化合物である。さ
らに、含水素ハロゲン化炭化水素（１）は、抽出媒体と
しても充分な相対揮発度を有する化合物である。The hydrogen-containing halogenated hydrocarbon (1) of the present invention is an extraction medium excellent in practicality. That is,
Since the hydrogen-containing halogenated hydrocarbon (1) has a structure containing one or more hydrogen atoms in the molecule, it is a compound that is not included in the specified CFCs and the like whose use is restricted after 1996. In addition, it is a compound that has a low impact on the environment because it has a low possibility of causing ozone layer depletion, and because the number of hydrogen atoms in the molecule is less than the number of carbon atoms + 1 It is a compound without dots. Further, the hydrogen-containing halogenated hydrocarbon (1) is a compound having a sufficient relative volatility as an extraction medium.
【００２０】本発明の含水素ハロゲン化炭化水素（１）
としては、ジクロロフルオロエタン類、ジクロロトリフ
ルオロエタン類、またはジクロロペンタフルオロプロパ
ン類が好ましい。また、含水素ハロゲン化炭化水素
（１）は、１種または２種以上を使用でき、通常の場合
は１種が好ましい。Hydrogen-containing halogenated hydrocarbon of the present invention (1)
As the above, dichlorofluoroethanes, dichlorotrifluoroethanes, or dichloropentafluoropropanes are preferable. The hydrogen-containing halogenated hydrocarbon (1) may be used alone or in combination of two or more kinds, and in the usual case, one kind is preferable.
【００２１】含水素ハロゲン化炭化水素（１）の特に好
ましい具体例を以下に挙げるがこれらに限定されない。
１，１−ジクロロ−１−フルオロエタン（Ｒ−１４１
ｂ）、２，２−ジクロロ−１，１，１−トリフルオロエ
タン（Ｒ−１２３）、１，２−ジクロロ−１，１，２−
トリフルオロエタン（Ｒ−１２３ａ）、３，３−ジクロ
ロ−１，１，１，２，２−ペンタフルオロプロパン（Ｒ
−２２５ｃａ）、１，３−ジクロロ−１，１，２，２，
３−ペンタフルオロプロパン（Ｒ−２２５ｃｂ）など。Particularly preferred specific examples of the hydrogen-containing halogenated hydrocarbon (1) are shown below, but the invention is not limited thereto.
1,1-dichloro-1-fluoroethane (R-141
b), 2,2-dichloro-1,1,1-trifluoroethane (R-123), 1,2-dichloro-1,1,2-
Trifluoroethane (R-123a), 3,3-dichloro-1,1,1,2,2-pentafluoropropane (R
-225ca), 1,3-dichloro-1,1,2,2,
3-pentafluoropropane (R-225cb) and the like.
【００２２】本発明においては、本質的にＨＦＰＯとＨ
ＦＰからなる混合物に、含水素ハロゲン化炭化水素
（１）の少なくとも１種を接触させることによって、Ｈ
ＦＰＯを分離し回収する。つぎにＨＦＰを含む含水素ハ
ロゲン化炭化水素（１）を加熱することにより、ＨＦＰ
を発生させ回収する。In the present invention, essentially HFPO and H
H is obtained by contacting a mixture of FP with at least one hydrogen-containing halogenated hydrocarbon (1).
Separate and collect FPO. Next, by heating the hydrogen-containing halogenated hydrocarbon (1) containing HFP,
Is generated and collected.
【００２３】本質的にＨＦＰＯとＨＦＰからなる混合物
に、含水素ハロゲン化炭化水素（１）の少なくとも一種
を接触させる操作方法としては、特に限定されない。し
かし、工業的に実施する場合には、以下の方法で連続的
に実施するのが好ましい。The operation method of bringing at least one of the hydrogen-containing halogenated hydrocarbon (1) into contact with the mixture essentially consisting of HFPO and HFP is not particularly limited. However, when it is carried out industrially, it is preferably carried out continuously by the following method.
【００２４】すなわち、２０〜８０段の理論段数を有す
る蒸留塔を準備し、該蒸留塔の中段に本質的にＨＦＰＯ
とＨＦＰからなる混合物を供給する。そして、蒸留塔頂
付近に含水素ハロゲン化炭化水素（１）を供給し、上部
から下部へ流す。含水素ハロゲン化炭化水素（１）によ
り少なく溶解するＨＦＰＯは、濃縮された状態で蒸留塔
頂部より除かれる。一方、ＨＦＰに富んだ含水素ハロゲ
ン化炭化水素（１）は、理論段数が通常１０〜５０段の
別の蒸留塔に導かれ、ＨＦＰと抽出媒体とに分離され
る。That is, a distillation column having a theoretical plate number of 20 to 80 is prepared, and HFPO is essentially contained in the middle stage of the distillation column.
And HFP. Then, the hydrogen-containing halogenated hydrocarbon (1) is supplied near the top of the distillation column and flows from the upper part to the lower part. HFPO, which is less soluble in the hydrogen-containing halogenated hydrocarbon (1), is removed from the top of the distillation column in a concentrated state. On the other hand, the hydrogen-containing halogenated hydrocarbon (1) rich in HFP is introduced into another distillation column having a theoretical plate number of usually 10 to 50 and separated into HFP and an extraction medium.
【００２５】別の蒸留塔で分離した含水素ハロゲン化炭
化水素（１）は、再び冷却されて、吸収塔の頂部に再循
環する。蒸留塔の形式は、充填塔型または泡鐘塔型が好
ましい。The hydrogen-containing halogenated hydrocarbon (1) separated in another distillation column is cooled again and recycled to the top of the absorption column. The type of distillation column is preferably a packed column type or a bubble column type.
【００２６】ＨＦＰとＨＦＰＯの混合物に接触させる含
水素ハロゲン化炭化水素（１）の量は、ＨＦＰとＨＦＰ
Ｏの混合物の１重量部に対して１〜１０００重量部程度
が好ましく、特に５〜５０重量部程度が好ましい。The amount of the hydrogen-containing halogenated hydrocarbon (1) to be contacted with the mixture of HFP and HFPO is HFP and HFP.
The amount is preferably about 1 to 1000 parts by weight, and particularly preferably about 5 to 50 parts by weight, relative to 1 part by weight of the O mixture.
【００２７】本質的にＨＦＰＯとＨＦＰからなる混合物
に、含水素ハロゲン化炭化水素（１）を接触させる際の
圧力は特に限定されず、最大圧力がＨＦＰとＨＦＰＯの
液化圧力未満であればよく、通常は、０．５〜１０気圧
程度（絶対圧) が好ましい。また、温度も特に限定され
ず、使用する含水素ハロゲン化炭化水素（１）によって
異なるものであり、通常は−２０〜１５０℃程度であ
る。The pressure for contacting the hydrogen-containing halogenated hydrocarbon (1) with the mixture essentially consisting of HFPO and HFP is not particularly limited, and the maximum pressure may be less than the liquefaction pressure of HFP and HFPO, Usually, about 0.5 to 10 atm (absolute pressure) is preferable. The temperature is also not particularly limited, and varies depending on the hydrogen-containing halogenated hydrocarbon (1) used, and is usually about -20 to 150 ° C.
【００２８】また、含水素ハロゲン化炭化水素（１）を
加熱してＨＦＰを発生させる際の圧力および温度も特に
限定されず、温度は、含水素ハロゲン化炭化水素（１）
の還流温度程度が好ましい。The pressure and temperature for heating the hydrogen-containing halogenated hydrocarbon (1) to generate HFP are also not particularly limited, and the temperature is the hydrogen-containing halogenated hydrocarbon (1).
A reflux temperature of about is preferable.
【００２９】[0029]
【実施例】以下に、本発明の実施例（例１〜４）および
比較例（例５〜１０）を挙げて具体的に説明するが、こ
れらによって本発明は限定されない。なお、以下の例に
おいては、抽出溶媒としての有効性をＨＦＰとＨＦＰＯ
の相対揮発度、リサイクル時の安定性をｐＨ試験紙によ
る溶媒酸分発生の有無、安全性を引火点を用いて評価し
た。EXAMPLES The present invention will be specifically described below with reference to Examples (Examples 1 to 4) and Comparative Examples (Examples 5 to 10) of the present invention, but the present invention is not limited thereto. In addition, in the following examples, the effectiveness as an extraction solvent was evaluated by using HFP and HFPO.
The relative volatility and stability at the time of recycling were evaluated by the presence or absence of generation of solvent acid content by pH test paper, and the safety was evaluated using the flash point.
【００３０】［相対揮発度の測定方法］オスマー型の加
圧平衡蒸留装置を用いて、表１に示す量のＨＦＰ、ＨＦ
ＰＯ、およびＲ−１４１ｂなどの抽出媒体を仕込み、釜
を加熱し、３〜６時間循環させた。その後、気相部の凝
縮液と釜の液相部分の液を採取し、ガスクロマトグラフ
により、ＨＦＰＯとＨＦＰのモル比を測定し、ＨＦＰに
対するＨＦＰＯの相対揮発度を求めた。[Measurement Method of Relative Volatility] Using an Osmer type pressure equilibrium distillation apparatus, the amounts of HFP and HF shown in Table 1 were used.
Extraction media such as PO and R-141b were charged, the kettle was heated and circulated for 3-6 hours. Then, the condensate of the gas phase and the liquid of the liquid phase of the kettle were sampled, the molar ratio of HFPO and HFP was measured by gas chromatography, and the relative volatility of HFPO to HFP was determined.
【００３１】［例１］オスマー型の加圧平衡蒸留装置を
用いて、Ｒ−１４１ｂの存在下に、ＨＦＰおよびＨＦＰ
Ｏの気液平衡を液相中のＨＦＰＯモル分率０．３５で求
めた結果、相対揮発度は１．２９であった。Example 1 Using an Osmer type pressure equilibrium distillation apparatus, HFP and HFP were obtained in the presence of R-141b.
The vapor-liquid equilibrium of O was determined at a HFPO mole fraction in the liquid phase of 0.35, and as a result, the relative volatility was 1.29.
【００３２】抽出蒸留システムは、図１に示すように、
抽出蒸留塔と溶剤回収塔の２塔から構成されるものを用
いた。抽出蒸留塔はさらに、溶剤回収部、濃縮部、回収
部の３つに分割される。The extractive distillation system, as shown in FIG.
A column composed of two columns, an extractive distillation column and a solvent recovery column, was used. The extractive distillation column is further divided into a solvent recovery section, a concentration section, and a recovery section.
【００３３】溶剤回収部の段数約５段、濃縮部の段数約
１１段、回収部約９段の蒸留塔に、ＨＦＰＯとＨＦＰの
１：１モル比混合物を濃縮部下部から毎時１５０ｇで連
続的に供給し、また、溶剤回収部下部よりＲ−１４１ｂ
を毎時５８００ｇ送り込み、塔底より毎時５８７２ｇ、
塔頂より毎時７８ｇで連続的に抜き出し、還流比１０に
制御しつつ抽出蒸留を行った。このときの系内の圧力は
２．７ｋｇＧ／ｃｍ2であり、塔頂温度は７℃、塔底温
度は７５℃であった。A 1: 1 molar ratio mixture of HFPO and HFP was continuously fed from the bottom of the concentration section at 150 g / hr to a distillation column having about 5 stages of solvent recovery section, about 11 stages of concentration section and about 9 stages of recovery section. R-141b from the bottom of the solvent recovery section
5800 g / h, and 5872 g / h from the bottom of the tower,
It was continuously withdrawn from the top of the column at 78 g / h, and extraction distillation was carried out while controlling the reflux ratio to 10. At this time, the pressure in the system was 2.7 kgG / cm 2 , the column top temperature was 7 ° C, and the column bottom temperature was 75 ° C.
【００３４】塔頂と塔底から試料を採取して分析した結
果、抽出媒体を除くＨＦＰＯとＨＦＰのモル分率で、塔
頂からは８９％のＨＦＰＯが得られ、塔底からは９０％
のＨＦＰが得られた。As a result of collecting and analyzing samples from the top and bottom of the column, 89% HFPO was obtained from the top and 90% from the bottom in terms of the molar fraction of HFPO and HFP excluding the extraction medium.
HFP was obtained.
【００３５】塔底より得られる高濃度のＨＦＰをモル分
率で１％溶解しているＲ−１４１ｂを約８段の段数をも
つ溶剤回収塔の下から第３段目に供給し、還流比を１０
に制御しながら回収蒸留を行った。このとき系内の圧力
は１．５ｋｇＧ／ｃｍ2 であり、塔頂温度は−８℃、塔
底温度は６２℃であった。R-141b, in which a high concentration of HFP obtained from the bottom of the column is dissolved by 1% in a mole fraction, is supplied to the third stage from the bottom of the solvent recovery column having about 8 stages, and the reflux ratio is set. 10
The recovery distillation was carried out while controlling the above. At this time, the pressure in the system was 1.5 kgG / cm 2 , the tower top temperature was −8 ° C., and the tower bottom temperature was 62 ° C.
【００３６】塔頂と塔底から試料を採取してガスクロマ
トグラフで分析した結果、塔頂からはモル分率で９９．
９９９％以上の純度でＨＦＰとＨＦＰＯの混合物が毎時
７２ｇで得られ、塔底からはモル分率で９９．９％以上
のＲ−１４１ｂが毎時５８００ｇで得られた。このＲ−
１４１ｂに酸分の発生は認められなかった。得られたＲ
−１４１ｂを抽出蒸留塔へ再循環させた。Samples were collected from the top and bottom of the column and analyzed by gas chromatography, and as a result, the molar fraction from the top was 99.
A mixture of HFP and HFPO having a purity of 999% or more was obtained at 72 g / hr, and R-141b having a molar fraction of 99.9% or more was obtained at 5800 g / hr from the column bottom. This R-
No generation of acid content was found in 141b. R obtained
-141b was recycled to the extractive distillation column.
【００３７】［例２〜４］表１に示す抽出媒体をそれぞ
れ用いて相対揮発度を求めた。また、例１と同一の装置
および方法で抽出蒸留を行った。結果を表１に示す。抽
出媒体は、いずれも引火点を持たないものである。Examples 2 to 4 Relative volatility was determined using each of the extraction media shown in Table 1. In addition, extractive distillation was performed using the same apparatus and method as in Example 1. The results are shown in Table 1. None of the extraction media has a flash point.
【００３８】［例５〜１０］表１に示す抽出媒体をそれ
ぞれ用いて相対揮発度を求めた。また、例１と同一の装
置および方法で抽出蒸留を行った。結果を表１に示す。
四塩化炭素は、オゾン層破壊の疑いがある化合物とし
て、使用が規制されている。また１，２−ジクロロエタ
ン、トルエン、ジイソプロピルエーテルは、いずれも引
火点を有する化合物である。[Examples 5-10] The relative volatility was determined using each of the extraction media shown in Table 1. In addition, extractive distillation was performed using the same apparatus and method as in Example 1. The results are shown in Table 1.
The use of carbon tetrachloride is regulated as a compound suspected of depleting the ozone layer. Further, 1,2-dichloroethane, toluene and diisopropyl ether are all compounds having a flash point.
【００３９】[0039]
【表１】 [Table 1]
【００４０】[0040]
【発明の効果】本発明によれば、従来の抽出媒体と同様
の相対揮発度を有する抽出媒体によりＨＦＰＯおよびＨ
ＦＰの抽出蒸留ができる。本発明の抽出媒体は安定剤を
添加しなくても安定であり、ＨＦＰＯおよびＨＦＰと反
応するおそれもなく、分離効果にも優れ、引火点の問題
もない。また、容易に入手でき、かつ環境に対しての影
響の少ない化合物であり、規制を受けていないものであ
る。したがって、本発明は実用的であり、操作が容易
で、分離効果にも優れた方法である。EFFECTS OF THE INVENTION According to the present invention, HFPO and H are obtained by using an extraction medium having a relative volatility similar to that of conventional extraction media.
Extractive distillation of FP is possible. The extraction medium of the present invention is stable without adding a stabilizer, has no risk of reacting with HFPO and HFP, has an excellent separation effect, and has no flash point problem. In addition, they are compounds that are easily available and have little impact on the environment, and are not regulated. Therefore, the present invention is a method that is practical, easy to operate, and excellent in separation effect.
【図１】実施例の抽出蒸留システムのプロセスフローチ
ャートFIG. 1 is a process flowchart of an extractive distillation system according to an embodiment.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 江畑 研一 神奈川県横浜市神奈川区羽沢町1150番地 旭硝子株式会社中央研究所内 ─────────────────────────────────────────────────── --- Continuation of the front page (72) Inventor Kenichi Ebata 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory
Claims (4)
ドとヘキサフルオロプロピレンからなる混合物に、一般
式（１）で表される含水素ハロゲン化炭化水素の少なく
とも１種を接触させて、ヘキサフルオロプロピレンオキ
シドを分離回収し、つぎにヘキサフルオロプロピレンを
含む含水素ハロゲン化炭化水素を加熱してヘキサフルオ
ロプロピレンを発生させ回収することを特徴とする、ヘ
キサフルオロプロピレンオキシドとヘキサフルオロプロ
ピレンの分離方法。 【化１】Ｃn Ｈa Ｃｌb Ｆc （１） ただし、式（１）において、ｎは２〜６の整数、ａは１
≦ａ≦ｎ＋１を満たす整数、ｂは１≦ｂ≦２ｎを満たす
整数、ｃは１≦ｃ≦２ｎを満たす整数であり、ａ＋ｂ＋
ｃ＝２ｎ＋２である。1. A mixture consisting essentially of hexafluoropropylene oxide and hexafluoropropylene is contacted with at least one hydrogen-containing halogenated hydrocarbon represented by the general formula (1) to give hexafluoropropylene oxide. A method for separating hexafluoropropylene oxide and hexafluoropropylene, which comprises separating and recovering, and then heating a hydrogen-containing halogenated hydrocarbon containing hexafluoropropylene to generate and recover hexafluoropropylene. Embedded image C n H a Cl b F c (1) where n is an integer of 2 to 6 and a is 1
An integer that satisfies ≦ a ≦ n + 1, b is an integer that satisfies 1 ≦ b ≦ 2n, c is an integer that satisfies 1 ≦ c ≦ 2n, and a + b +
c = 2n + 2.
ドとヘキサフルオロプロピレンからなる混合物に、一般
式（１）で表される含水素ハロゲン化炭化水素の少なく
とも１種を接触させて、ヘキサフルオロプロピレンオキ
シドを分離回収することを特徴とする、ヘキサフルオロ
プロピレンオキシドの分離方法。 【化２】Ｃn Ｈa Ｃｌb Ｆc （１） ただし、式（１）において、ｎは２〜６の整数、ａは１
≦ａ≦ｎ＋１を満たす整数、ｂは１≦ｂ≦２ｎを満たす
整数、ｃは１≦ｃ≦２ｎを満たす整数であり、ａ＋ｂ＋
ｃ＝２ｎ＋２である。2. A mixture consisting essentially of hexafluoropropylene oxide and hexafluoropropylene is contacted with at least one hydrogen-containing halogenated hydrocarbon represented by the general formula (1) to give hexafluoropropylene oxide. A method for separating hexafluoropropylene oxide, which comprises separating and recovering. ## STR00002 ## C n H a Cl b F c (1) where n is an integer of 2 to 6 and a is 1 in the formula (1).
An integer that satisfies ≦ a ≦ n + 1, b is an integer that satisfies 1 ≦ b ≦ 2n, c is an integer that satisfies 1 ≦ c ≦ 2n, and a + b +
c = 2n + 2.
炭化水素が、ジクロロフルオロエタン類、ジクロロトリ
フルオロエタン類、または、ジクロロペンタフルオロプ
ロパン類である請求項１または２の分離方法。3. The separation method according to claim 1, wherein the hydrogen-containing halogenated hydrocarbon represented by the general formula (1) is dichlorofluoroethanes, dichlorotrifluoroethanes or dichloropentafluoropropanes. .
炭化水素が、１，１−ジクロロ−１−フルオロエタンで
ある請求項１または２の分離方法。4. The method according to claim 1, wherein the hydrogen-containing halogenated hydrocarbon represented by the general formula (1) is 1,1-dichloro-1-fluoroethane.
Priority Applications (1)
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|---|---|---|---|
| JP17376295A JP3785652B2 (en) | 1995-07-10 | 1995-07-10 | Separation method of hexafluoropropylene oxide and hexafluoropropylene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17376295A JP3785652B2 (en) | 1995-07-10 | 1995-07-10 | Separation method of hexafluoropropylene oxide and hexafluoropropylene |
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| Publication Number | Publication Date |
|---|---|
| JPH0920765A true JPH0920765A (en) | 1997-01-21 |
| JP3785652B2 JP3785652B2 (en) | 2006-06-14 |
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ID=15966681
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|---|---|---|---|
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| Country | Link |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040879A (en) * | 2001-07-31 | 2003-02-13 | Asahi Glass Co Ltd | Method for producing hexafluoropropylene oxide |
| WO2010106865A1 (en) * | 2009-03-18 | 2010-09-23 | ダイキン工業株式会社 | Method for separating hexafluoropropylene oxide from hexafluoropropylene |
| US8299280B2 (en) | 2008-10-27 | 2012-10-30 | University Of Kwazulu-Natal | Recovery of components making up a liquid mixture |
| US10370313B2 (en) | 2016-02-26 | 2019-08-06 | AGC Inc. | Manufacturing method of purified 1-chloro-2,3,3,3-Tetrafluoropropene and purified 1-chloro-2,3,3,3-tetrafluoropropene (Z) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528719A (en) | 2006-10-24 | 2009-09-09 | 大金工业株式会社 | Process for production of hexafluoropropylene oxide |
-
1995
- 1995-07-10 JP JP17376295A patent/JP3785652B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003040879A (en) * | 2001-07-31 | 2003-02-13 | Asahi Glass Co Ltd | Method for producing hexafluoropropylene oxide |
| US8299280B2 (en) | 2008-10-27 | 2012-10-30 | University Of Kwazulu-Natal | Recovery of components making up a liquid mixture |
| WO2010106865A1 (en) * | 2009-03-18 | 2010-09-23 | ダイキン工業株式会社 | Method for separating hexafluoropropylene oxide from hexafluoropropylene |
| JP5267657B2 (en) * | 2009-03-18 | 2013-08-21 | ダイキン工業株式会社 | Separation method of hexafluoropropylene oxide and hexafluoropropylene |
| US8877017B2 (en) | 2009-03-18 | 2014-11-04 | Daikin Industries, Ltd. | Method for separating hexafluoropropylene oxide from hexafluoropropylene |
| US10370313B2 (en) | 2016-02-26 | 2019-08-06 | AGC Inc. | Manufacturing method of purified 1-chloro-2,3,3,3-Tetrafluoropropene and purified 1-chloro-2,3,3,3-tetrafluoropropene (Z) |
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| Publication number | Publication date |
|---|---|
| JP3785652B2 (en) | 2006-06-14 |
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