JP2013231120A - Azeotropic or azeotrope-like composition, and method for producing 2,3,3,3-tetrafluoro propene or hexafluoropropene - Google Patents
Azeotropic or azeotrope-like composition, and method for producing 2,3,3,3-tetrafluoro propene or hexafluoropropene Download PDFInfo
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本発明は、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンからなる共沸または共沸様組成物、および、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの混合物から２，３，３，３−テトラフルオロプロペンまたはヘキサフルオロプロペンを製造する方法に関する。 The present invention relates to an azeotropic or azeotrope-like composition comprising 2,3,3,3-tetrafluoropropene and hexafluoropropene, and a mixture of 2,3,3,3-tetrafluoropropene and hexafluoropropene. The present invention relates to a method for producing 2,3,3,3-tetrafluoropropene or hexafluoropropene.
２，３，３，３−テトラフルオロプロペン（ＨＦＯ−１２３４ｙｆ）は、温室効果ガスである１，１，１，２−テトラフルオロエタン（ＨＦＣ−１３４ａ）に代わる新しい冷媒として、近年大きな期待が寄せられている。なお、本明細書において、ハロゲン化炭化水素については化合物名の後の括弧内にその化合物の略称を記すが、本明細書では必要に応じて化合物名に代えてその略称を用いる。 In recent years, 2,3,3,3-tetrafluoropropene (HFO-1234yf) has been highly expected as a new refrigerant to replace 1,1,1,2-tetrafluoroethane (HFC-134a), which is a greenhouse gas. It has been. In the present specification, for halogenated hydrocarbons, the abbreviations of the compounds are described in parentheses after the compound names. In the present specification, the abbreviations are used instead of the compound names as necessary.
ＨＦＯ−１２３４ｙｆの製造方法としては、例えば、１，１−ジクロロ−２，２，３，３，３−ペンタフルオロプロパン（ＨＣＦＣ−２２５ｃａ）を相間移動触媒の存在下にアルカリ水溶液で脱フッ化水素させて得られる１，１−ジクロロ−２，３，３，３−テトラフルオロプロペン（ＣＦＯ−１２１４ｙａ）を原料とし、水素により還元して製造する方法が知られている。 As a method for producing HFO-1234yf, for example, 1,1-dichloro-2,2,3,3,3-pentafluoropropane (HCFC-225ca) is dehydrofluorinated with an alkaline aqueous solution in the presence of a phase transfer catalyst. A method is known in which 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) obtained by reduction is used as a raw material and is reduced by hydrogen.
しかし、上記の方法では、反応工程数が多く、中間生成物や最終生成物の蒸留精製が必要である。一方、クロロフルオロカーボン類を含む原料から熱分解を伴う１回の反応でＨＦＯ−１２３４ｙｆを製造する方法が提案されている。このような方法として、例えば、特許文献１には、クロロメタン（Ｒ４０）とクロロジフルオロメタン（Ｒ２２）および／またはテトラフルオロエチレン（ＴＦＥ）との混合物を加熱分解して、ＨＦＯ−１２３４ｙｆを得る方法が提示されている。Ｒ４０とＲ２２および／またはＴＦＥとの混合物は、熱分解および脱塩化水素反応によりジフルオロカルベン（Ｆ２Ｃ：）とＲ４０とを含む反応混合物を生成し、これらの反応混合物は、直接付加反応して、あるいは１種または２種以上の中間体を経て、テトラフルオロプロペン、特にＨＦＯ−１２３４ｙｆへと転化されると考えられる。 However, in the above method, the number of reaction steps is large, and distillation purification of intermediate products and final products is necessary. On the other hand, a method for producing HFO-1234yf from a raw material containing chlorofluorocarbons by a single reaction involving thermal decomposition has been proposed. As such a method, for example, Patent Document 1 discloses a method of obtaining HFO-1234yf by thermally decomposing a mixture of chloromethane (R40) and chlorodifluoromethane (R22) and / or tetrafluoroethylene (TFE). Is presented. The mixture of R40 and R22 and / or TFE produces a reaction mixture containing difluorocarbene (F 2 C :) and R40 by thermal decomposition and dehydrochlorination reaction, and these reaction mixtures are subjected to direct addition reaction. Or, via one or more intermediates, is believed to be converted to tetrafluoropropene, particularly HFO-1234yf.
本発明者らの検討によると、上記方法によりＨＦＯ−１２３４ｙｆを製造する場合、得られる反応混合物中には、目的物質のＨＦＯ−１２３４ｙｆや未反応原料以外に、ＴＦＥ、１，１−ジフルオロエチレン（ＶｄＦ）、クロロトリフルオロエチレン（ＣＴＦＥ）、ヘキサフルオロプロペン（ＨＦＰ）、オクタフルオロシクロブタン（ＲＣ３１８）等の多種の副生物が含まれ、その生成量は製造条件により様々であることがわかった。また、これら副生物のうちでもＲ２２のように熱分解してＦ２Ｃ：を発生しうる含フッ素化合物であるＴＦＥ、ＨＦＰ、ＣＴＦＥ、ＲＣ３１８等は、上記熱分解を伴う合成反応へのリサイクル使用がＨＦＯ−１２３４ｙｆの生産効率を上げる点で有効であると考えられる。さらに、反応混合物から、目的物質のＨＦＯ−１２３４ｙｆとは別にＴＦＥ、ＶｄＦ、ＨＦＰ、ＣＴＦＥ等を単離すれば、これらは各種フッ素樹脂原料として有効利用できる。
ここで、目的物質のＨＦＯ−１２３４ｙｆや上記各種有用成分を上記反応混合物中から取り出す方法として、蒸留が挙げられるが、副生物のうちでもＨＦＰは、ＨＦＯ−１２３４ｙｆと沸点が近いことが知られており、両者の分離は容易でないと想定された。
According to the study by the present inventors, when HFO-1234yf is produced by the above-mentioned method, in the obtained reaction mixture, in addition to the target substance HFO-1234yf and unreacted raw materials, TFE, 1,1-difluoroethylene ( Various by-products such as VdF), chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), and octafluorocyclobutane (RC318) were included, and it was found that the amount produced varies depending on the production conditions. Among these by-products, TFE, HFP, CTFE, RC318, etc., which are fluorine-containing compounds that can be thermally decomposed to generate F 2 C: like R22, are recycled for use in the synthesis reaction involving the above thermal decomposition. Is considered effective in increasing the production efficiency of HFO-1234yf. Furthermore, if TFE, VdF, HFP, CTFE, etc. are isolated from the reaction mixture separately from the target substance HFO-1234yf, these can be effectively used as various fluororesin raw materials.
Here, as a method of taking out the target substance HFO-1234yf and the various useful components from the reaction mixture, distillation can be mentioned. Among the by-products, HFP is known to have a boiling point close to that of HFO-1234yf. Therefore, it was assumed that separation of the two was not easy.
本発明は、上記観点からなされたものであり、２，３，３，３−テトラフルオロプロペン（ＨＦＯ−１２３４ｙｆ）およびヘキサフルオロプロペン（ＨＦＰ）を含む混合物から、ＨＦＯ−１２３４ｙｆおよびＨＦＰを効率よく分離する方法を提供することを目的とする。 The present invention has been made from the above viewpoint, and efficiently separates HFO-1234yf and HFP from a mixture containing 2,3,3,3-tetrafluoropropene (HFO-1234yf) and hexafluoropropene (HFP). It aims to provide a way to do.
本発明は、２，３，３，３−テトラフルオロプロペンを２５．９モル％、ヘキサフルオロプロペンを７４．１モル％含有する共沸組成物を提供する。
また、本発明は、２，３，３，３−テトラフルオロプロペンを７６．９〜８．７モル％、ヘキサフルオロプロペンを２３．１〜９１．３モル％含有する共沸様組成物を提供する。
The present invention provides an azeotropic composition containing 25.9 mol% 2,3,3,3-tetrafluoropropene and 74.1 mol% hexafluoropropene.
The present invention also provides an azeotrope-like composition containing 76.9 to 8.7 mol% of 2,3,3,3-tetrafluoropropene and 23.1 to 91.3 mol% of hexafluoropropene. To do.
本発明は、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンを含む混合組成物であって、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量が前記混合組成物中９０モル％以上であり、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンとの含有割合がモル比で２，３，３，３−テトラフルオロプロペン／ヘキサフルオロプロペン＝２５．９／７４．１である混合組成物を提供する。
本発明は、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンを含む混合組成物であって、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量が前記混合組成物中９０モル％以上であり、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンとの含有割合がモル比で２，３，３，３−テトラフルオロプロペン／ヘキサフルオロプロペン＝７６．９／２３．１〜８．７／９１．３である混合組成物を提供する。
本発明は、上記本発明の共沸組成物または共沸様組成物を含む冷媒を提供する。
The present invention is a mixed composition containing 2,3,3,3-tetrafluoropropene and hexafluoropropene, wherein the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is the mixed composition And the content ratio of 2,3,3,3-tetrafluoropropene to hexafluoropropene is 2,3,3,3-tetrafluoropropene / hexafluoropropene = 25. A mixed composition is provided that is 9 / 74.1.
The present invention is a mixed composition containing 2,3,3,3-tetrafluoropropene and hexafluoropropene, wherein the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is the mixed composition The content ratio of 2,3,3,3-tetrafluoropropene and hexafluoropropene is 2,3,3,3-tetrafluoropropene / hexafluoropropene = 76. A mixed composition is provided that is 9 / 23.1 to 8.7 / 91.3.
The present invention provides a refrigerant comprising the azeotropic composition or azeotrope-like composition of the present invention.
本発明は、主として２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンからなる初期混合物であって、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合がモル比で２５．９％を超える初期混合物を蒸留して、
２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合より低い第１留分と、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合より高い第２留分に分離し、前記第２留分からヘキサフルオロプロペン濃度が低下した２，３，３，３−テトラフルオロプロペンを得る工程を含む、２，３，３，３−テトラフルオロプロペンの製造方法を提供する。
The present invention is an initial mixture mainly consisting of 2,3,3,3-tetrafluoropropene and hexafluoropropene, wherein 2,3,2 in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene. The initial mixture in which the content of 3,3,3-tetrafluoropropene exceeds 25.9% in molar ratio is distilled,
The content of 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is such that 2,3,3,3-tetrafluoro in the initial mixture First fraction lower than the content of 2,3,3,3-tetrafluoropropene in the total amount of propene and hexafluoropropene, and the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene The content of 2,3,3,3-tetrafluoropropene in the initial mixture is 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene in the initial mixture. 2,3,3,3-tetrafluoro, which was separated into a second fraction higher than the content of tetrafluoropropene and the hexafluoropropene concentration was reduced from the second fraction It comprises obtaining propene, to provide a method for manufacturing a 2,3,3,3-tetrafluoropropene.
さらに、本発明は、主として２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンからなる初期混合物であって、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合がモル比で７４．１％を超える初期混合物を蒸留して、
２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合より低い第１留分と、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合より高い第２留分に分離し、前記第２留分から２，３，３，３−テトラフルオロプロペンの濃度が低下したヘキサフルオロプロペンを得る工程を含む、ヘキサフルオロプロペンの製造方法を提供する。
Furthermore, the present invention is an initial mixture mainly consisting of 2,3,3,3-tetrafluoropropene and hexafluoropropene, wherein the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is An initial mixture having a hexafluoropropene content exceeding 74.1% in molar ratio is distilled,
The content of hexafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene in the initial mixture. A first fraction lower than the content of hexafluoropropene in the mixture, and the content of hexafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is 2 in the initial mixture. The second fraction is separated into a second fraction having a higher content of hexafluoropropene in the total amount of 3,3,3-tetrafluoropropene and hexafluoropropene, and 2,3,3,3-tetrafluoropropene is separated from the second fraction. A process for producing hexafluoropropene, comprising a step of obtaining hexafluoropropene having a reduced concentration of Subjected to.
本発明によれば、２，３，３，３−テトラフルオロプロペン（ＨＦＯ−１２３４ｙｆ）およびヘキサフルオロプロペン（ＨＦＰ）を含む混合物から、ＨＦＯ−１２３４ｙｆおよびＨＦＰを効率よく分離することができる。 According to the present invention, HFO-1234yf and HFP can be efficiently separated from a mixture containing 2,3,3,3-tetrafluoropropene (HFO-1234yf) and hexafluoropropene (HFP).
以下、本発明の実施の形態について説明する。
［共沸組成物］
本発明のＨＦＯ−１２３４ｙｆとＨＦＰからなる共沸組成物は、ＨＦＯ−１２３４ｙｆの含有割合が２５．９モル％であり、ＨＦＰの含有割合が７４．１モル％の組成物であって、圧力１．０１１×１０６Ｐａにおける沸点が４１．３℃である。共沸組成物は、該組成物を繰り返し蒸発、凝縮させた場合、組成変化がなく、冷媒等の用途に用いた場合に、極めて安定して性能が得られる利点がある。なお、共沸組成物は、以下の式で示される比揮発度が１．００である。
Embodiments of the present invention will be described below.
[Azeotropic composition]
The azeotropic composition comprising HFO-1234yf and HFP of the present invention is a composition having an HFO-1234yf content of 25.9 mol% and an HFP content of 74.1 mol%, and a pressure of 1 The boiling point at 011 × 10 6 Pa is 41.3 ° C. An azeotropic composition is advantageous in that, when the composition is repeatedly evaporated and condensed, there is no change in composition, and when used in applications such as refrigerants, performance is obtained extremely stably. The azeotropic composition has a relative volatility represented by the following formula of 1.00.
（比揮発度を求める式）
比揮発度＝（気相部におけるＨＦＯ−１２３４ｙｆのモル％／気相部におけるＨＦＰのモル％）／（液相部におけるＨＦＯ−１２３４ｙｆのモル％／液相部におけるＨＦＰのモル％）
(Formula for calculating relative volatility)
Specific volatility = (mol% of HFO-1234yf in gas phase / mol% of HFP in gas phase) / (mol% of HFO-1234yf in liquid phase / mol% of HFP in liquid phase)
［共沸様組成物］
本発明のＨＦＯ−１２３４ｙｆとＨＦＰからなる共沸様組成物は、ＨＦＯ−１２３４ｙｆの含有割合が７６．９〜８．７モル％であり、ＨＦＰの含有割合が２３．１〜９１．３モル％の組成物である。蒸発、凝縮を繰り返した場合の組成の変動が小さい。なお、本明細書において、共沸様組成物とは、上記式で求められる比揮発度が１．００±０．１０の範囲にある組成物をいう。また、本発明のＨＦＯ−１２３４ｙｆとＨＦＰからなる共沸様組成物は、圧力が１．０１１×１０６Ｐａにおける沸点が４１〜４２℃である。
[Azeotropic composition]
In the azeotrope-like composition comprising HFO-1234yf and HFP of the present invention, the content of HFO-1234yf is 76.9 to 8.7 mol%, and the content of HFP is 23.1 to 91.3 mol%. Of the composition. Fluctuation in composition when evaporation and condensation are repeated is small. In the present specification, the azeotrope-like composition refers to a composition having a relative volatility determined by the above formula in the range of 1.00 ± 0.10. In addition, the azeotrope-like composition comprising HFO-1234yf and HFP of the present invention has a boiling point of 41 to 42 ° C. at a pressure of 1.011 × 10 6 Pa.
本発明の共沸様組成物は、上記本発明の共沸組成物とほぼ同等に取り扱え、冷媒等の用途に用いた場合に、共沸組成物と同等の安定した性能等が得られる利点がある。なお、以下の説明において共沸様組成物は、共沸組成物を含むものとして記載する。 The azeotrope-like composition of the present invention can be handled almost the same as the azeotrope composition of the present invention, and has the advantage that stable performance and the like equivalent to those of the azeotrope composition can be obtained when used for applications such as refrigerant. is there. In the following description, an azeotrope-like composition is described as including an azeotrope composition.
[混合組成物]
本発明の第１の実施形態の混合組成物は、ＨＦＯ−１２３４ｙｆとＨＦＰを含む混合組成物であって、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量が前記混合組成物中９０モル％以上であり、ＨＦＯ−１２３４ｙｆとＨＦＰとの含有割合がモル比でＨＦＯ−１２３４ｙｆ／ＨＦＰ＝２５．９／７４．１である。
[Mixed composition]
The mixed composition of the first embodiment of the present invention is a mixed composition containing HFO-1234yf and HFP, wherein the total amount of HFO-1234yf and HFP is 90 mol% or more in the mixed composition, and HFO The content ratio of −1234yf and HFP is HFO-1234yf / HFP = 25.9 / 74.1 in molar ratio.
本発明の第２の実施形態の混合組成物は、ＨＦＯ−１２３４ｙｆとＨＦＰを含む混合組成物であって、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量が前記混合組成物中９０モル％以上であり、ＨＦＯ−１２３４ｙｆとＨＦＰとの含有割合がモル比でＨＦＯ−１２３４ｙｆ／ＨＦＰ＝７６．９／２３．１〜８．７／９１．３である。 The mixed composition of the second embodiment of the present invention is a mixed composition containing HFO-1234yf and HFP, wherein the total amount of HFO-1234yf and HFP is 90 mol% or more in the mixed composition, and HFO The content ratio of −1234yf and HFP is HFO-1234yf / HFP = 76.9 / 23.1 to 8.7 / 91.3 in molar ratio.
本発明の混合組成物は、ＨＦＯ−１２３４ｙｆおよびＨＦＰ以外のその他の成分を１０モル％未満含んでいてもよい。上記その他の成分としては、ハイドロクロロカーボン類、ハイドロフルオロカーボン類、ハイドロクロロフルオロカーボン類、クロロフルオロカーボン類、フルオロカーボン類が挙げられる。具体的には、Ｒ２２、Ｒ４０、ＴＦＥ、ＲＣ３１８、ＣＴＦＥ、トリフルオロエチレン、ヘキサフルオロプロピレンオキサイド（ＨＦＰＯ）、ジフルオロエチレン、テトラフルオロエタン、トリフルオロプロペン、ジフルオロエタン、ヘプタフルオロプロペン、クロロジフルオロエチレン、クロロエチレン、クロロテトラフルオロエタン、クロロフルオロメタン、およびジフルオロメタンが挙げられる。上記その他の成分は５モル％以下が好ましく、３モル％以下がより好ましい。 The mixed composition of the present invention may contain less than 10 mol% of other components other than HFO-1234yf and HFP. Examples of the other components include hydrochlorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, and fluorocarbons. Specifically, R22, R40, TFE, RC318, CTFE, trifluoroethylene, hexafluoropropylene oxide (HFPO), difluoroethylene, tetrafluoroethane, trifluoropropene, difluoroethane, heptafluoropropene, chlorodifluoroethylene, chloroethylene , Chlorotetrafluoroethane, chlorofluoromethane, and difluoromethane. The other components are preferably 5 mol% or less, more preferably 3 mol% or less.
［冷媒］
本発明の冷媒は、本発明の共沸組成物または共沸様組成物を含有する。本発明の冷媒における本発明の共沸組成物または共沸様組成物の含有割合は８０質量％以上が好ましく、９０質量％以上がより好ましい。本発明の冷媒は、本発明の共沸組成物または共沸様組成物を含有することで冷媒の冷却性能の調節が可能である。本発明の冷媒としては、なかでも、本発明の共沸組成物または共沸様組成物で構成される冷媒が好ましい。
[Refrigerant]
The refrigerant of the present invention contains the azeotropic composition or azeotrope-like composition of the present invention. The content of the azeotropic composition or azeotrope-like composition of the present invention in the refrigerant of the present invention is preferably 80% by mass or more, and more preferably 90% by mass or more. The refrigerant of the present invention can adjust the cooling performance of the refrigerant by containing the azeotropic composition or azeotrope-like composition of the present invention. As the refrigerant of the present invention, a refrigerant composed of the azeotropic composition or azeotrope-like composition of the present invention is particularly preferable.
また、本発明の冷媒は、必要に応じて水捕捉剤、酸捕捉剤、酸化防止剤および安定剤を含有していてもよい。また、本発明の冷媒は、ポリアルキレングリコール（ＰＡＧ）、ポリオールエステル（ＰＯＥ）、ポリビニルエーテル（ＰＶＥ）、アルキルベンゼン、合成パラフィン、合成ナフテン、およびポリ（アルファ）オレフィンを含む、冷凍およびエアコンシステムに典型的に使用される潤滑油と併用できる。 Moreover, the refrigerant of the present invention may contain a water scavenger, an acid scavenger, an antioxidant and a stabilizer as necessary. The refrigerant of the present invention is also typical for refrigeration and air conditioning systems comprising polyalkylene glycol (PAG), polyol ester (POE), polyvinyl ether (PVE), alkylbenzene, synthetic paraffin, synthetic naphthene, and poly (alpha) olefin. Can be used in combination with commonly used lubricants.
［ＨＦＯ−１２３４ｙｆまたはＨＦＰの製造方法］
本発明は、主としてＨＦＯ−１２３４ｙｆとＨＦＰからなる初期混合物を蒸留する工程を利用して、該初期混合物中のＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆおよびＨＦＰの含有割合に応じて、高度に精製されたＨＦＯ−１２３４ｙｆ、または、高度に精製されたＨＦＰを、それぞれ製造する方法を提供する。
[Method for producing HFO-1234yf or HFP]
The present invention utilizes a step of distilling an initial mixture mainly composed of HFO-1234yf and HFP, and depending on the content ratio of HFO-1234yf and HFP in the total amount of HFO-1234yf and HFP in the initial mixture, Provided are methods for producing highly purified HFO-1234yf or highly purified HFP, respectively.
本発明の製造方法において、上記初期混合物中の、ＨＦＯ−１２３４ｙｆとＨＦＰの含有割合は、ＨＦＯ−１２３４ｙｆとＨＦＰが共沸組成物となる上記含有割合を除けばいかなる含有割合であってもよい。また、上記初期混合物としては、初期混合物中のＨＦＯ−１２３４ｙｆとＨＦＰの合計含有量が９０質量％以上、さらには９５質量％以上であるものが好ましい。
ここで、初期混合物における、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合がモル比で２５．９％を超える場合には、該初期混合物から、高度に精製されたＨＦＯ−１２３４ｙｆを製造できる。以下、この製造方法を、本発明の第１の実施形態の製造方法という。第１の実施形態の製造方法において、初期混合物における、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合はモル比で２５．９％を超え１００％未満であれば特に制限されない。
In the production method of the present invention, the content ratio of HFO-1234yf and HFP in the initial mixture may be any content ratio except the content ratio in which HFO-1234yf and HFP are azeotropic compositions. Moreover, as said initial mixture, the total content of HFO-1234yf and HFP in an initial mixture is 90 mass% or more, Furthermore, what is 95 mass% or more is preferable.
Here, when the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture exceeds 25.9% in molar ratio, highly purified HFO-1234yf from the initial mixture is used. Can be manufactured. Hereinafter, this manufacturing method is referred to as a manufacturing method according to the first embodiment of the present invention. In the production method of the first embodiment, the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture is not particularly limited as long as it exceeds 25.9% and is less than 100% in terms of molar ratio.
また、初期混合物における、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合がモル比で７４．１％を超える場合には、該初期混合物から、高度に精製されたＨＦＰを製造できる。以下、この製造方法を、本発明の第２の実施形態の製造方法という。第２の実施形態の製造方法において、初期混合物における、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合はモル比で７４．１％を超え１００％未満であれば特に制限されない。 Further, when the content ratio of HFP in the total amount of HFO-1234yf and HFP in the initial mixture exceeds 74.1% in molar ratio, highly purified HFP can be produced from the initial mixture. Hereinafter, this manufacturing method is referred to as a manufacturing method according to the second embodiment of the present invention. In the production method of the second embodiment, the content ratio of HFP in the total amount of HFO-1234yf and HFP in the initial mixture is not particularly limited as long as the molar ratio exceeds 74.1% and is less than 100%.
本発明の第１の実施形態の製造方法および第２の実施形態の製造方法における初期混合物としては、それぞれ上記条件を満たす初期混合物であれば特に制限されないが、例えば、Ｒ４０と、熱分解してＦ２Ｃ：を発生しうる含フッ素化合物、具体的には、Ｒ２２、ＴＦＥ、ＨＦＰ、ＲＣ３１８、ＣＴＦＥ、トリフルオロエチレン、ＨＦＰＯ等、との熱分解を伴うＨＦＯ−１２３４ｙｆの合成反応により得られる反応混合物から、蒸留により分取されたＨＦＯ−１２３４ｙｆおよびＨＦＰからなる留分やＨＦＯ−１２３４ｙｆおよびＨＦＰを主成分とする留分等が挙げられる。 The initial mixture in the manufacturing method of the first embodiment and the manufacturing method of the second embodiment of the present invention is not particularly limited as long as it is an initial mixture that satisfies the above conditions. Reaction obtained by synthesis reaction of HFO-1234yf accompanied by thermal decomposition with fluorine-containing compound capable of generating F 2 C :, specifically, R22, TFE, HFP, RC318, CTFE, trifluoroethylene, HFPO, etc. Examples of the mixture include a fraction composed of HFO-1234yf and HFP fractionated by distillation, a fraction mainly composed of HFO-1234yf and HFP, and the like.
なお、上記ＨＦＯ−１２３４ｙｆの合成反応により得られる上記留分を、本発明の製造方法において、蒸留工程に供する初期混合物として用いる場合には、必ずしもＨＦＯ−１２３４ｙｆおよびＨＦＰ以外の成分が完全に除去されている必要はない。すなわち、該留分（初期混合物）は、ＨＦＯ−１２３４ｙｆおよびＨＦＰ以外のその他の化合物を本発明の効果を損なわない範囲で含有していてもよく、具体的には、Ｒ２２、Ｒ４０、ＴＦＥ、ＲＣ３１８、ＣＴＦＥ、トリフルオロエチレン、ＨＦＰＯ、ジフルオロエチレン、テトラフルオロエタン、トリフルオロプロペン、ジフルオロエタン、ヘプタフルオロプロペン、クロロジフルオロエチレン、クロロエチレン、クロロテトラフルオロエタン、クロロフルオロメタン、ジフルオロメタン等を含有していてもよい。上記その他の化合物の含有量は、初期混合物中１０モル％未満が好ましい。 When the fraction obtained by the synthesis reaction of HFO-1234yf is used as an initial mixture for the distillation step in the production method of the present invention, components other than HFO-1234yf and HFP are not necessarily completely removed. You don't have to. That is, the fraction (initial mixture) may contain other compounds other than HFO-1234yf and HFP as long as the effects of the present invention are not impaired. Specifically, R22, R40, TFE, RC318. , CTFE, trifluoroethylene, HFPO, difluoroethylene, tetrafluoroethane, trifluoropropene, difluoroethane, heptafluoropropene, chlorodifluoroethylene, chloroethylene, chlorotetrafluoroethane, chlorofluoromethane, difluoromethane, etc. Also good. The content of the other compounds is preferably less than 10 mol% in the initial mixture.
本発明の第１の実施形態の製造方法は、主としてＨＦＯ−１２３４ｙｆとＨＦＰからなる初期混合物であって、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合がモル比で２５．９％を超える初期混合物を蒸留して、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、前記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より低い第１留分と、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、前記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より高い第２留分に分離し、前記第２留分からＨＦＰ濃度が低下したＨＦＯ−１２３４ｙｆを得る工程を含む。 The production method of the first embodiment of the present invention is an initial mixture mainly composed of HFO-1234yf and HFP, and the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP is 25.9 in molar ratio. % Of the initial mixture is distilled, and the content of HFO-1234yf in the total amount of HFO-1234yf and HFP is lower than the content of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture. The first fraction and the second fraction in which the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP is higher than the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture. And obtaining HFO-1234yf having a reduced HFP concentration from the second fraction. No.
第１の実施形態における蒸留の条件としては、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、上記記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より低い第１留分と、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より高い第２留分に分離できる条件であれば特に制限されない。用いる蒸留塔としては、中空の蒸留塔でもよく、多段式の蒸留塔であってもよい。蒸留はバッチ式で行われても、連続式で行われてもよい。蒸留の圧力条件は、大気圧〜５ＭＰａとすることが好ましい。温度条件としては、塔頂温度として−３０〜７０℃が好ましい。 As distillation conditions in the first embodiment, the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP is the content of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture. The first fraction lower than the ratio and the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP is higher than the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture. The conditions are not particularly limited as long as they can be separated into two fractions. The distillation column used may be a hollow distillation column or a multistage distillation column. Distillation may be performed batchwise or continuously. The distillation pressure condition is preferably atmospheric pressure to 5 MPa. As temperature conditions, -30-70 degreeC is preferable as tower top temperature.
第１の実施形態の製造方法における蒸留を、多段式の蒸留塔を用いて行う場合、通常、上記初期混合物は蒸留塔の中段から供給され、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、上記記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より低い第１留分が蒸留塔の塔頂からの留出液として得られる。また、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より高い第２留分が塔底からの缶出液として得られる。 When the distillation in the production method of the first embodiment is performed using a multistage distillation column, the initial mixture is usually supplied from the middle column of the distillation column, and HFO-1234yf in the total amount of HFO-1234yf and HFP. The 1st fraction whose content rate is lower than the content rate of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture is obtained as a distillate from the top of the distillation column. Further, the second fraction in which the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP is higher than the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture is from the tower bottom. Obtained as a bottomed liquid.
これは、上記の通り、圧力１．０１１×１０６ＰａにおけるＨＦＯ−１２３４ｙｆとＨＦＰの共沸様組成物の沸点が４１〜４２℃であり、またＨＦＯ−１２３４ｙｆの沸点は４３℃であることによる。塔頂から留出液として得られる、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、上記記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より低い第１留分は、通常、ＨＦＯ−１２３４ｙｆとＨＦＰの共沸様組成物を含む混合組成物として得られる。このような第１留分に対して、必要に応じてさらに蒸留を繰り返し行うことで、最終的にＨＦＯ−１２３４ｙｆとＨＦＰの共沸組成物を得ることも可能である。 This is because, as described above, the boiling point of the azeotrope-like composition of HFO-1234yf and HFP at a pressure of 1.011 × 10 6 Pa is 41 to 42 ° C., and the boiling point of HFO-1234yf is 43 ° C. . The content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP obtained as a distillate from the top of the column is higher than the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture. The lower first fraction is usually obtained as a mixed composition comprising an azeotrope-like composition of HFO-1234yf and HFP. It is also possible to finally obtain an azeotropic composition of HFO-1234yf and HFP by repeatedly performing distillation on the first fraction as necessary.
また、この場合、塔底から缶出液として得られるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合より高い第２留分は、必要に応じてさらに蒸留を繰り返すことで、よりＨＦＰ濃度が低い高純度のＨＦＯ−１２３４ｙｆとすることができる。
このようにして本発明の第１の実施形態の製造方法により得られる、高純度のＨＦＯ−１２３４ｙｆは、冷媒としての使用が期待できる。
In this case, the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP obtained as a bottoms from the bottom of the column is such that the content of HFO-1234yf in the total amount of HFO-1234yf and HFP in the initial mixture is The second fraction having a higher content ratio can be made into high-purity HFO-1234yf having a lower HFP concentration by further repeating distillation as necessary.
Thus, the high purity HFO-1234yf obtained by the manufacturing method of the first embodiment of the present invention can be expected to be used as a refrigerant.
本発明の第２の実施形態の製造方法は、主としてＨＦＯ−１２３４ｙｆとＨＦＰからなる初期混合物であって、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合がモル比で７４．１％を超える初期混合物を蒸留して、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、前記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より低い第１留分と、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、前記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より高い第２留分に分離し、前記第２留分からＨＦＯ−１２３４ｙｆの濃度が低下したＨＦＰを得る工程を含む。 The production method of the second embodiment of the present invention is an initial mixture mainly composed of HFO-1234yf and HFP, and the content ratio of HFP in the total amount of HFO-1234yf and HFP is 74.1% in molar ratio. A first fraction having a HFP-1234yf and HFP content in the total amount of HFO-1234yf and HFP lower than the HFP content in the total amount of HFO-1234yf and HFP in the initial mixture; The HFP-1234yf and the HFP content in the total amount of HFP are separated into a second fraction that is higher than the HFP content in the total amount of HFO-1234yf and HFP in the initial mixture, and the HFO is separated from the second fraction. Including a step of obtaining HFP having a reduced concentration of −1234yf.
第２の実施形態における蒸留の条件としては、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より低い第１留分と、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より高い第２留分に分離できる条件であれば特に制限されない。用いる蒸留塔としては、中空の蒸留塔でもよく、多段式の蒸留塔であってもよい。蒸留はバッチ式で行われても、連続式で行われてもよい。蒸留の圧力条件は、大気圧〜５ＭＰａとすることが好ましい。温度条件としては、塔頂温度として−３０〜７０℃が好ましい。 As distillation conditions in the second embodiment, the content ratio of HFP in the total amount of HFO-1234yf and HFP is lower than the content ratio of HFP in the total amount of HFO-1234yf and HFP in the initial mixture. The HFP-1234yf and HFP content ratio in the total amount of HFO-1234yf and HFP can be separated into a second fraction that is higher than the HFP content ratio in the total amount of HFO-1234yf and HFP in the initial mixture. There is no particular limitation. The distillation column used may be a hollow distillation column or a multistage distillation column. Distillation may be performed batchwise or continuously. The distillation pressure condition is preferably atmospheric pressure to 5 MPa. As temperature conditions, -30-70 degreeC is preferable as tower top temperature.
第２の実施形態の製造方法における蒸留を、多段式の蒸留塔を用いて行う場合、通常、上記出発材料は蒸留塔の中段から供給され、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より低い第１留分が蒸留塔の塔頂からの留出液として得られる。また、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より高い第２留分が塔底からの缶出液として得られる。 When the distillation in the production method of the second embodiment is performed using a multistage distillation column, the starting material is usually supplied from the middle stage of the distillation column, and the HFP content in the total amount of HFO-1234yf and HFP is included. A first fraction whose ratio is lower than the content ratio of HFP in the total amount of HFO-1234yf and HFP in the initial mixture is obtained as a distillate from the top of the distillation column. In addition, the second fraction in which the HFP content ratio in the total amount of HFO-1234yf and HFP is higher than the HFP content ratio in the total amount of HFO-1234yf and HFP in the initial mixture is the bottom liquid from the tower bottom. As obtained.
これは、上記の通り、圧力１．０１１×１０６ＰａにおけるＨＦＯ−１２３４ｙｆとＨＦＰの共沸様組成物の沸点が４１〜４２℃であり、またＨＦＰの沸点は４４℃であることによる。塔頂から留出液として得られる、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より低い第１留分は、通常、ＨＦＯ−１２３４ｙｆとＨＦＰの共沸様組成物を含む混合組成物として得られる。このような第１留分に対して、必要に応じてさらに蒸留を繰り返し行うことで、最終的にＨＦＯ−１２３４ｙｆとＨＦＰの共沸組成物を得ることも可能である。 This is because the boiling point of the azeotrope-like composition of HFO-1234yf and HFP at a pressure of 1.011 × 10 6 Pa is 41 to 42 ° C. and the boiling point of HFP is 44 ° C. as described above. The first fraction obtained as a distillate from the top of the column, wherein the HFP content in the total amount of HFO-1234yf and HFP is lower than the HFP content in the total amount of HFO-1234yf and HFP in the initial mixture. Is usually obtained as a mixed composition comprising an azeotrope-like composition of HFO-1234yf and HFP. It is also possible to finally obtain an azeotropic composition of HFO-1234yf and HFP by repeatedly performing distillation on the first fraction as necessary.
また、この場合、塔底から缶出液として得られるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合が、上記初期混合物におけるＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合より高い第２留分は、必要に応じてさらに蒸留を繰り返すことで、よりＨＦＯ−１２３４ｙｆ濃度が低い高純度のＨＦＰとすることができる。
このようにして本発明の第２の実施形態の製造方法により得られる、高純度のＨＦＰは、例えば、上記Ｒ４０と、Ｒ２２等の熱分解してＦ２Ｃ：を発生しうる含フッ素化合物との、熱分解を伴うＨＦＯ−１２３４ｙｆの合成反応における、原料成分（熱分解してＦ２Ｃ：を発生しうる含フッ素化合物）として使用できる。高純度のＨＦＰは、さらに、ＦＥＰ（ＴＦＥ−ＨＦＰ共重合体）、ＶｄＦ−ＨＦＰ共重合体等のフッ素樹脂原料としても有用である。
In this case, the content ratio of HFP in the total amount of HFO-1234yf and HFP obtained as bottoms from the tower bottom is higher than the content ratio of HFP in the total amount of HFO-1234yf and HFP in the initial mixture. The second fraction can be made into high-purity HFP having a lower HFO-1234yf concentration by further repeating distillation as necessary.
Thus, the high purity HFP obtained by the production method of the second embodiment of the present invention is, for example, the above R40 and a fluorine-containing compound capable of generating F 2 C: by thermal decomposition of R22 and the like. In the synthesis reaction of HFO-1234yf accompanied by thermal decomposition, it can be used as a raw material component (a fluorine-containing compound capable of generating F 2 C: upon thermal decomposition). High-purity HFP is also useful as a raw material for fluororesins such as FEP (TFE-HFP copolymer) and VdF-HFP copolymer.
以下、実施例によって本発明を詳細に説明するが、本発明はこれらに限定されない。
＜気液平衡の測定＞
ＨＦＯ−１２３４ｙｆとＨＦＰを表１に示す質量比で混合して得られる混合物１〜７を、５００ｍＬの圧力計付きオートクレーブに入れ、圧力が１．０１１×１０６Ｐａとなるように徐々に外部ヒータによって加熱した。オートクレーブ内の圧力が所定の１．０１１×１０６Ｐａとなった後、一定時間保持してオートクレーブ内の組成を安定化させた。気相および液相から混合物１〜７のサンプルを採取し、ガスクロマトグラフィーでＨＦＯ−１２３４ｙｆとＨＦＰを分析し、両者の組成比を測定した。両者の組成比から上に説明した比揮発度を求める式により比揮発度を求めた。
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
<Measurement of vapor-liquid equilibrium>
Mixtures 1 to 7 obtained by mixing HFO-1234yf and HFP at a mass ratio shown in Table 1 are put into a 500 mL autoclave with a pressure gauge, and gradually an external heater so that the pressure becomes 1.011 × 10 6 Pa. Heated by. After the pressure in the autoclave reached a predetermined value of 1.011 × 10 6 Pa, the composition in the autoclave was stabilized by maintaining for a certain period of time. Samples of the mixtures 1 to 7 were taken from the gas phase and the liquid phase, HFO-1234yf and HFP were analyzed by gas chromatography, and the composition ratio of both was measured. The relative volatility was obtained from the formula for obtaining the relative volatility described above from the composition ratio of the two.
表１に混合物１〜７の気相部、液相部の組成および比揮発度をそれぞれ示した。混合物１〜７のようにオートクレーブに仕込む混合物中のＨＦＰの比率を少しずつ増加させたところ、表１に示すように比揮発度の値が徐々に増加した。混合物４の場合、気相および液相の組成は、ＨＦＯ−１２３４ｙｆが２５．９モル％、ＨＦＰが７４．１モル％で一致した。このときの気相温度は４１．３℃であり、比揮発度の値が１．００となった。ＨＦＰの比率をさらに増加させると比揮発度は１．００以上の値へと増加した。 Table 1 shows the composition and relative volatility of the gas phase part and the liquid phase part of the mixtures 1 to 7, respectively. When the ratio of HFP in the mixture charged into the autoclave was gradually increased like the mixtures 1 to 7, the relative volatility value gradually increased as shown in Table 1. In the case of the mixture 4, the composition of the gas phase and the liquid phase was the same at 25.9 mol% for HFO-1234yf and 74.1 mol% for HFP. The gas phase temperature at this time was 41.3 ° C., and the relative volatility value was 1.00. When the HFP ratio was further increased, the relative volatility increased to a value of 1.00 or higher.
表１には示されていないが、比揮発度が１．００±０．１０となる範囲のＨＦＯ−１２３４ｙｆとＨＦＰの組成を、上記同様にしてＨＦＯ−１２３４ｙｆとＨＦＰの組成を漸次変化させながら気相と液相における両者のモル％を測定することで求めた。結果は、圧力が１．０１１×１０６Ｐａの場合に、ＨＦＯ−１２３４ｙｆとＨＦＰの含有割合が、ＨＦＯ−１２３４ｙｆ／ＨＦＰで示されるモル比で７６．９／２３．１〜８．７／９１．３の組成物において、比揮発度が１．００±０．１０であった。 Although not shown in Table 1, the composition of HFO-1234yf and HFP in the range where the relative volatility is 1.00 ± 0.10 is changed in the same manner as above, while the composition of HFO-1234yf and HFP is gradually changed. It calculated | required by measuring mol% of both in a gaseous phase and a liquid phase. As a result, when the pressure is 1.011 × 10 6 Pa, the content ratio of HFO-1234yf and HFP is 76.9 / 23.1 to 8.7 / 91 in terms of a molar ratio represented by HFO-1234yf / HFP. In the composition of .3, the relative volatility was 1.00 ± 0.10.
［実施例１］
初期混合物として、ＨＦＯ−１２３４ｙｆとＨＦＰからなる混合物であり、該混合物全量中ＨＦＯ−１２３４ｙｆを７５モル％、ＨＦＰを２５モル％含む初期混合物Ａを準備する。この初期混合物Ａを３００ｇ／ｈｒの速度で高さ２ｍ、内径４．５ｃｍ蒸留塔に供給し、運転圧力０．５ＭＰａ、塔頂温度１９℃で連続的に蒸留を行う。塔頂より１１７ｇ／ｈｒの速度で留出液を抜き出し、塔底より１８３ｇ／ｈｒの速度で缶出液を抜き出す。抜き出した留出液、缶出液のそれぞれについてガスクロマトグラフィーで組成を分析する。留出液および缶出液の組成の分析結果を下記表２にモル％で示す。
[Example 1]
As an initial mixture, an initial mixture A comprising HFO-1234yf and HFP and containing 75 mol% HFO-1234yf and 25 mol% HFP in the total amount of the mixture is prepared. This initial mixture A is fed to a distillation column having a height of 2 m and an inner diameter of 4.5 cm at a rate of 300 g / hr, and continuously distilled at an operating pressure of 0.5 MPa and a column top temperature of 19 ° C. A distillate is withdrawn from the top of the column at a rate of 117 g / hr, and a bottoms is withdrawn from the bottom of the column at a rate of 183 g / hr. The composition of each of the extracted distillate and bottoms is analyzed by gas chromatography. The analysis results of the composition of the distillate and bottoms are shown in Table 2 in mol%.
表２に示すように、初期混合物として、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＯ−１２３４ｙｆの含有割合がモル比で２５．９％を超える混合物を用いて蒸留を行えば、塔頂からは、該初期混合物よりＨＦＰ濃度が高くＨＦＯ−１２３４ｙｆ濃度が低い、ＨＦＯ−１２３４ｙｆとＨＦＰの共沸様組成物が得られ、塔底からは該初期混合物よりＨＦＰ濃度が低く、純度の高いＨＦＯ−１２３４ｙｆが得られることがわかる。 As shown in Table 2, if distillation is performed using a mixture in which the content ratio of HFO-1234yf in the total amount of HFO-1234yf and HFP exceeds 25.9% as the initial mixture, , An azeotrope-like composition of HFO-1234yf and HFP having a higher HFP concentration and a lower HFO-1234yf concentration than the initial mixture is obtained, and HFO-1234yf having a higher HFP concentration and higher purity than the initial mixture is obtained from the bottom of the column. It can be seen that
［実施例２］
初期混合物として、ＨＦＯ−１２３４ｙｆとＨＦＰからなる混合物であり、該混合物全量中ＨＦＯ−１２３４ｙｆを１０モル％、ＨＦＰを９０モル％含む初期混合物Ｂを準備する。この初期混合物Ｂを３００ｇ／ｈｒの速度で高さ２ｍ、内径４．５ｃｍの精留塔に供給し、運転圧力０．５ＭＰａ、塔頂温度１９℃で連続的に蒸留を行う。塔頂より１１６ｇ／ｈｒの速度で留出液を抜き出し、塔底より１８４ｇ／ｈｒの速度で缶出液を抜き出す。抜き出した留出液、缶出液のそれぞれについてガスクロマトグラフィーで組成を分析する。留出液および缶出液の組成の分析結果を下記表２にモル％で示す。
[Example 2]
As an initial mixture, an initial mixture B comprising HFO-1234yf and HFP and containing 10 mol% HFO-1234yf and 90 mol% HFP in the total amount of the mixture is prepared. This initial mixture B is supplied to a rectification column having a height of 2 m and an inner diameter of 4.5 cm at a rate of 300 g / hr, and continuously distilled at an operating pressure of 0.5 MPa and a column top temperature of 19 ° C. The distillate is withdrawn from the top of the column at a rate of 116 g / hr, and the bottoms is withdrawn from the bottom of the column at a rate of 184 g / hr. The composition of each of the extracted distillate and bottoms is analyzed by gas chromatography. The analysis results of the composition of the distillate and bottoms are shown in Table 2 in mol%.
表２に示すように、初期混合物として、ＨＦＯ−１２３４ｙｆとＨＦＰの合計量中のＨＦＰの含有割合がモル比で７４．１％を超える混合物を用いて蒸留を行えば、塔頂からは、該混合物よりＨＦＯ−１２３４ｙｆ濃度が高くＨＦＰ濃度が低い、ＨＦＯ−１２３４ｙｆとＨＦＰの共沸様組成物が得られ、塔底からはＨＦＯ−１２３４ｙｆ濃度が低く、純度の高いＨＦＰが得られることがわかる。 As shown in Table 2, if distillation is performed using a mixture in which the content ratio of HFP in the total amount of HFO-1234yf and HFP exceeds 74.1% as an initial mixture, It can be seen that an azeotrope-like composition of HFO-1234yf and HFP having a higher HFO-1234yf concentration and a lower HFP concentration than the mixture is obtained, and a high-purity HFP is obtained from the tower bottom with a lower HFO-1234yf concentration.
Claims (7)
２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合より低い第１留分と、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中の２，３，３，３−テトラフルオロプロペンの含有割合より高い第２留分に分離し、前記第２留分からヘキサフルオロプロペン濃度が低下した２，３，３，３−テトラフルオロプロペンを得る工程を含む、２，３，３，３−テトラフルオロプロペンの製造方法。 An initial mixture consisting primarily of 2,3,3,3-tetrafluoropropene and hexafluoropropene, wherein 2,3,3,3 in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene The initial mixture in which the content ratio of 3-tetrafluoropropene exceeds 25.9% by mole is distilled,
The content of 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is such that 2,3,3,3-tetrafluoro in the initial mixture First fraction lower than the content of 2,3,3,3-tetrafluoropropene in the total amount of propene and hexafluoropropene, and the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene The content of 2,3,3,3-tetrafluoropropene in the initial mixture is 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene in the initial mixture. 2,3,3,3-tetrafluoro, which was separated into a second fraction higher than the content of tetrafluoropropene and the hexafluoropropene concentration was reduced from the second fraction It comprises obtaining propene, 2,3,3,3 method for producing tetrafluoropropene.
２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合より低い第１留分と、２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合が、前記初期混合物における２，３，３，３−テトラフルオロプロペンとヘキサフルオロプロペンの合計量中のヘキサフルオロプロペンの含有割合より高い第２留分に分離し、前記第２留分から２，３，３，３−テトラフルオロプロペンの濃度が低下したヘキサフルオロプロペンを得る工程を含む、ヘキサフルオロプロペンの製造方法。 The initial mixture mainly consisting of 2,3,3,3-tetrafluoropropene and hexafluoropropene, the content ratio of hexafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene Distilling the initial mixture with a molar ratio of more than 74.1%,
The content of hexafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene in the initial mixture. A first fraction lower than the content of hexafluoropropene in the mixture, and the content of hexafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and hexafluoropropene is 2 in the initial mixture. The second fraction is separated into a second fraction having a higher content of hexafluoropropene in the total amount of 3,3,3-tetrafluoropropene and hexafluoropropene, and 2,3,3,3-tetrafluoropropene is separated from the second fraction. A process for producing hexafluoropropene, which comprises the step of obtaining hexafluoropropene having a reduced concentration of.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019021726A1 (en) * | 2017-07-24 | 2019-01-31 | ダイキン工業株式会社 | Refrigerant composition |
| JP2019023278A (en) * | 2017-07-24 | 2019-02-14 | ダイキン工業株式会社 | Refrigerant composition |
| WO2020081363A1 (en) * | 2018-10-15 | 2020-04-23 | Honeywell International Inc. | Azeotrope or azeotrope-like compositions of trifluoroiodomethane (cf3i) and hexafluoropropene (hfp) |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011513227A (en) * | 2008-02-21 | 2011-04-28 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for separating 2,3,3,3-tetrafluoropropene from hydrogen fluoride by azeotropic distillation |
| JP2011520016A (en) * | 2008-05-07 | 2011-07-14 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Composition comprising 1,1,1,2,3-pentafluoropropane or 2,3,3,3-tetrafluoropropene |
| US20120261252A1 (en) * | 2008-02-21 | 2012-10-18 | E.I. Du Pont De Nemours And Company | Processes for separation of 2,3,3,3-tetrafluoropropene from hydrogen fluoride by azeotropic distillation |
| WO2013154059A1 (en) * | 2012-04-09 | 2013-10-17 | 旭硝子株式会社 | Azeotropic or azeotrope−like composition, and method for producing 2,3,3,3-tetrafluoropropene or chloromethane |
| JP2013230998A (en) * | 2012-04-27 | 2013-11-14 | Asahi Glass Co Ltd | Azeotrope or azeotrope-like composition, and method of manufacturing chloromethane or hexafluoropropene |
| JP2013230997A (en) * | 2012-04-27 | 2013-11-14 | Asahi Glass Co Ltd | Azeotrope or azeotrope-like composition, and method of manufacturing chloromethane or chlorotrifluoroethylene |
| JP2013230996A (en) * | 2012-04-27 | 2013-11-14 | Asahi Glass Co Ltd | Azeotrope or azeotrope-like composition, and method of manufacturing 2,3,3,3-tetrafluoro propene or chlorotrifluoroethylene |
-
2012
- 2012-04-27 JP JP2012103599A patent/JP6011008B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011513227A (en) * | 2008-02-21 | 2011-04-28 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Method for separating 2,3,3,3-tetrafluoropropene from hydrogen fluoride by azeotropic distillation |
| US20120261252A1 (en) * | 2008-02-21 | 2012-10-18 | E.I. Du Pont De Nemours And Company | Processes for separation of 2,3,3,3-tetrafluoropropene from hydrogen fluoride by azeotropic distillation |
| JP2011520016A (en) * | 2008-05-07 | 2011-07-14 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Composition comprising 1,1,1,2,3-pentafluoropropane or 2,3,3,3-tetrafluoropropene |
| US20120165578A1 (en) * | 2008-05-07 | 2012-06-28 | E. I. Du Pont De Nemours And Company | Compositions comprising 1,1,1,2,3-pentafluoropropane or 2,3,3,3- tetrafluoropropene |
| WO2013154059A1 (en) * | 2012-04-09 | 2013-10-17 | 旭硝子株式会社 | Azeotropic or azeotrope−like composition, and method for producing 2,3,3,3-tetrafluoropropene or chloromethane |
| JP2013230998A (en) * | 2012-04-27 | 2013-11-14 | Asahi Glass Co Ltd | Azeotrope or azeotrope-like composition, and method of manufacturing chloromethane or hexafluoropropene |
| JP2013230997A (en) * | 2012-04-27 | 2013-11-14 | Asahi Glass Co Ltd | Azeotrope or azeotrope-like composition, and method of manufacturing chloromethane or chlorotrifluoroethylene |
| JP2013230996A (en) * | 2012-04-27 | 2013-11-14 | Asahi Glass Co Ltd | Azeotrope or azeotrope-like composition, and method of manufacturing 2,3,3,3-tetrafluoro propene or chlorotrifluoroethylene |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11091679B2 (en) * | 2017-07-24 | 2021-08-17 | Daikin Industries, Ltd. | Refrigerant composition |
| JP2019023278A (en) * | 2017-07-24 | 2019-02-14 | ダイキン工業株式会社 | Refrigerant composition |
| CN110945100A (en) * | 2017-07-24 | 2020-03-31 | 大金工业株式会社 | Refrigerant composition |
| WO2019021726A1 (en) * | 2017-07-24 | 2019-01-31 | ダイキン工業株式会社 | Refrigerant composition |
| US11447675B2 (en) | 2017-07-24 | 2022-09-20 | Daikin Industries, Ltd. | Refrigerant composition |
| EP3985079A1 (en) * | 2017-07-24 | 2022-04-20 | Daikin Industries, Ltd. | Refrigerant composition |
| WO2020081363A1 (en) * | 2018-10-15 | 2020-04-23 | Honeywell International Inc. | Azeotrope or azeotrope-like compositions of trifluoroiodomethane (cf3i) and hexafluoropropene (hfp) |
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| US11344761B2 (en) | 2018-10-15 | 2022-05-31 | Honeywell International Inc. | Azeotrope or azeotrope-like compositions of trifluoroiodomethane (CF3I) and 1,1,1,2,2,3,3,-heptafluoropropane (HFC-227ca) |
| EP3867330A4 (en) * | 2018-10-15 | 2022-07-13 | Honeywell International Inc. | Azeotrope or azeotrope-like compositions of trifluoroiodomethane (cf3i) and hexafluoropropene (hfp) |
| JP2021004231A (en) * | 2019-01-28 | 2021-01-14 | ダイキン工業株式会社 | Azeotropic composition containing 1,2-difluoroethylene or 1,1,2-trifluoroethylene and hydrogen fluoride |
| WO2020158668A1 (en) * | 2019-01-28 | 2020-08-06 | ダイキン工業株式会社 | Azeotropic composition containing 1,2-difluoroethylene or 1,1,2-trifluoroethylene and hydrogen fluoride |
| CN115975601A (en) * | 2023-01-09 | 2023-04-18 | 天津大学 | Ternary mixed working medium containing R1216 |
| CN115975601B (en) * | 2023-01-09 | 2023-09-12 | 天津大学 | Ternary mixed working medium containing R1216 |
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