JP2013230996A - Azeotrope or azeotrope-like composition, and method of manufacturing 2,3,3,3-tetrafluoro propene or chlorotrifluoroethylene - Google Patents

Azeotrope or azeotrope-like composition, and method of manufacturing 2,3,3,3-tetrafluoro propene or chlorotrifluoroethylene Download PDF

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JP2013230996A
JP2013230996A JP2012103600A JP2012103600A JP2013230996A JP 2013230996 A JP2013230996 A JP 2013230996A JP 2012103600 A JP2012103600 A JP 2012103600A JP 2012103600 A JP2012103600 A JP 2012103600A JP 2013230996 A JP2013230996 A JP 2013230996A
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hfo
chlorotrifluoroethylene
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tetrafluoropropene
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Shoji Furuta
昇二 古田
Tetsuo Otsuka
哲央 大塚
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AGC Inc
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Asahi Glass Co Ltd
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Abstract

PROBLEM TO BE SOLVED: To provide a method that efficiently separates HFO-1234yf and CTFE from a mixture including 2,3,3,3-tetrafluoro propene (HFO-1234yf) and chlorotrifluoroethylene (CTFE).SOLUTION: A method of manufacturing HFO-1234yf includes a process in which an azeotrope-like composition consisting of 23-91% by mol of HFO-1234yf and 77-9% by mol of CTFE, and an initial mixture including HFO-1234yf and CTFE in which a content of HFO-1234yf in the total amount thereof exceeds 49% by mol are distilled to be separated into a first fraction in which a content of HFO-1234yf in the total amount of HFO-1234yf and CTFE is lower than that of the initial mixture, and a second fraction in which a content of HFO-1234yf in the total amount of HFO-1234yf and CTFE is higher than that of the initial mixture, whereby HFO-1234yf in which a concentration of CTFE is lowered is obtained from the second fraction.

Description

本発明は、2,3,3,3−テトラフルオロプロペンとクロロトリフルオロエチレ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クロロトリフルオロエチレンの混合物から2,3,3,3−テトラフルオロプロペンまたはクロロトリフルオロエチレ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 chlorotrifluoroethylene, and 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene. The present invention relates to a process for producing 2,3,3,3-tetrafluoropropene or chlorotrifluoroethylene from a mixture.

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(FC:)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.

米国特許第2931840号明細書U.S. Pat. No. 2,931,840

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FC: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CTFE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, CTFE 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)およびクロロトリフルオロエチレン(CTFE)を含む混合物から、HFO−1234yfおよびCTFE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 converts HFO-1234yf and CTFE from a mixture containing 2,3,3,3-tetrafluoropropene (HFO-1234yf) and chlorotrifluoroethylene (CTFE). The object is to provide a method of separation.

本発明は、2,3,3,3−テトラフルオロプロペンを49モル%、クロロトリフルオロエチレンを51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23〜91モル%、クロロトリフルオロエチレンを77〜9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 49 mol% 2,3,3,3-tetrafluoropropene and 51 mol% chlorotrifluoroethylene.
The present invention also provides an azeotrope-like composition containing 23-91 mol% 2,3,3,3-tetrafluoropropene and 77-9 mol% chlorotrifluoroethylene.

本発明は、2,3,3,3−テトラフルオロプロペンとクロロトリフルオロエチレ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クロロトリフルオロエチレ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クロロトリフルオロエチレ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/クロロトリフルオロエチレン=49/51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クロロトリフルオロエチレ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クロロトリフルオロエチレ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クロロトリフルオロエチレ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/クロロトリフルオロエチレン=23/77〜91/9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 comprising 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, wherein the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is It is 90 mol% or more in the mixed composition, and the content ratio of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is 2,3,3,3-tetrafluoropropene / chlorotrifluoro in molar ratio. A blend composition is provided wherein ethylene = 49/51.
The present invention is a mixed composition comprising 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, wherein the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is It is 90 mol% or more in the mixed composition, and the content ratio of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is 2,3,3,3-tetrafluoropropene / chlorotrifluoro in molar ratio. A blend composition is provided wherein ethylene = 23/77 to 91/9.
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クロロトリフルオロエチレ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クロロトリフルオロエチレンの合計量中の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49%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クロロトリフルオロエチレンの合計量中の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クロロトリフルオロエチレンの合計量中の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クロロトリフルオロエチレンの合計量中の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クロロトリフルオロエチレンの合計量中の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留分からクロロトリフルオロエチレン濃度が低下した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 consisting primarily of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, in a total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene. The initial mixture in which the content ratio of 2,3,3,3-tetrafluoropropene exceeds 49% in molar ratio is distilled,
The content ratio of 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is 2,3,3,3-tetrafluoroethylene in the initial mixture. A first fraction lower than the content of 2,3,3,3-tetrafluoropropene in the total amount of fluoropropene and chlorotrifluoroethylene, and 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene Of 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and 2,3,3 in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene in the initial mixture. It was separated into a second fraction higher than the content of 3,3-tetrafluoropropene, and the chlorotrifluoroethylene concentration decreased from the second fraction. , 3-tetrafluoro including the step of 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クロロトリフルオロエチレ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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレンの含有割合がモル比で51%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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレンの含有割合が、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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレ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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレンの含有割合が、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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレ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クロロトリフルオロエチレンを得る工程を含む、クロロトリフルオロエチレンの製造方法を提供する。
Furthermore, the present invention is an initial mixture mainly composed of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, wherein the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene The initial mixture in which the content of chlorotrifluoroethylene in the mixture exceeds 51% by mole is distilled,
The content ratio of chlorotrifluoroethylene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene in the initial mixture. A first fraction lower than the content ratio of chlorotrifluoroethylene in the total amount of chlorotrifluoroethylene, and the content ratio of chlorotrifluoroethylene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, The initial mixture is separated into a second fraction higher than the content of chlorotrifluoroethylene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, and 2,3 from the second fraction. A step of obtaining chlorotrifluoroethylene having a reduced concentration of 1,3,3-tetrafluoropropene To provide a manufacturing method of chlorotrifluoroethylene.

本発明によれば、2,3,3,3−テトラフルオロプロペン(HFO−1234yf)およびクロロトリフルオロエチレン(CTFE)を含む混合物から、HFO−1234yfおよびCTFEを効率よく分離することができる。   According to the present invention, HFO-1234yf and CTFE can be efficiently separated from a mixture containing 2,3,3,3-tetrafluoropropene (HFO-1234yf) and chlorotrifluoroethylene (CTFE).

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CTFEからなる共沸組成物は、HFO−1234yfの含有割合が49モル%であり、CTFEの含有割合が51モル%の組成物であって、圧力1.011×10Paにおける沸点が41.7℃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 CTFE of the present invention is a composition having a HFO-1234yf content of 49 mol% and a CTFE content of 51 mol%, and a pressure of 1.011 × 10 6. The boiling point at 6 Pa is 41.7 ° 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CTFEのモル%)/(液相部におけるHFO−1234yfのモル%/液相部におけるCTFEのモル%)
(Formula for calculating relative volatility)
Specific volatility = (mol% of HFO-1234yf in gas phase / mol% of CTFE in gas phase) / (mol% of HFO-1234yf in liquid phase / mol% of CTFE in liquid phase)

[共沸様組成物]
本発明のHFO−1234yfとCTFEからなる共沸様組成物は、HFO−1234yfの含有割合が23〜91モル%であり、CTFEの含有割合が77〜9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CTFEからなる共沸様組成物は、圧力が1.011×10Paにおける沸点が41〜42.5℃である。
[Azeotropic composition]
The azeotrope-like composition comprising HFO-1234yf and CTFE of the present invention is a composition having a HFO-1234yf content of 23-91 mol% and a CTFE content of 77-9 mol%. 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 CTFE of the present invention has a boiling point of 41 to 42.5 ° 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CTFEを含む混合組成物であって、HFO−1234yfとCTFEの合計量が前記混合組成物中90モル%以上であり、HFO−1234yfとCTFEとの含有割合がモル比でHFO−1234yf/CTFE=49/51である。
[Mixed composition]
The mixed composition of the first embodiment of the present invention is a mixed composition containing HFO-1234yf and CTFE, wherein the total amount of HFO-1234yf and CTFE is 90 mol% or more in the mixed composition, and HFO The content ratio of −1234yf and CTFE is HFO-1234yf / CTFE = 49/51 in molar ratio.

本発明の第2の実施形態の混合組成物は、HFO−1234yfとCTFEを含む混合組成物であって、HFO−1234yfとCTFEの合計量が前記混合組成物中90モル%以上であり、HFO−1234yfとCTFEとの含有割合がモル比でHFO−1234yf/CTFE=23/77〜91/9である。   The mixed composition of the second embodiment of the present invention is a mixed composition containing HFO-1234yf and CTFE, wherein the total amount of HFO-1234yf and CTFE is 90 mol% or more in the mixed composition, and HFO The content ratio of −1234yf and CTFE is HFO-1234yf / CTFE = 23/77 to 91/9 in molar ratio.

本発明の混合組成物は、HFO−1234yfおよびCTFE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、HFP、RC318、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 CTFE. Examples of the other components include hydrochlorocarbons, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, and fluorocarbons. Specifically, R22, R40, TFE, HFP, RC318, 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CTFEの製造方法]
本発明は、主としてHFO−1234yfとCTFE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CTFEの合計量中のHFO−1234yfおよびCTFE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CTFEを、それぞれ製造する方法を提供する。
[Method for producing HFO-1234yf or CTFE]
The present invention uses a step of distilling an initial mixture mainly composed of HFO-1234yf and CTFE, and depending on the content ratio of HFO-1234yf and CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture, Provided is a method for producing highly purified HFO-1234yf or highly purified CTFE, 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CTFEの含有割合は、HFO−1234yfとCTFE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CTFE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CTFEの合計量中のHFO−1234yfの含有割合がモル比で49%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CTFEの合計量中のHFO−1234yfの含有割合はモル比で49%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 CTFE in the initial mixture may be any content ratio except for the content ratio in which HFO-1234yf and CTFE become an azeotropic composition. Moreover, as said initial mixture, the thing whose sum total content of HFO-1234yf and CTFE in an initial mixture is 90 mass% or more, Furthermore, 95 mass% or more is preferable.
Here, when the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE in the initial mixture exceeds 49% in molar ratio, highly purified HFO-1234yf is produced from the initial mixture. it can. 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 CTFE in the initial mixture is not particularly limited as long as it is more than 49% and less than 100% in terms of molar ratio.

また、初期混合物における、HFO−1234yfとCTFEの合計量中のCTFEの含有割合がモル比で51%を超える場合には、該初期混合物から、高度に精製されたCTFE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CTFEの合計量中のCTFEの含有割合はモル比で51%を超え100%未満であれば特に制限されない。   Further, when the content ratio of CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture exceeds 51% in terms of molar ratio, highly purified CTFE 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 CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture is not particularly limited as long as the molar ratio is more than 51% and 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FC: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CTFEからなる留分やHFO−1234yfおよびCTFE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 CTFE fractionated by distillation, a fraction mainly composed of HFO-1234yf and CTFE, 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CTFE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CTFE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、HFP、RC318、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 CTFE 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 CTFE as long as the effects of the present invention are not impaired. Specifically, R22, R40, TFE, HFP , RC318, 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CTFEからなる初期混合物であって、HFO−1234yfとCTFEの合計量中のHFO−1234yfの含有割合がモル比で49%を超える初期混合物を蒸留して、HFO−1234yfとCTFE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CTFE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CTFE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CTFE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CTFE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 CTFE, and the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE is 49% in terms of molar ratio. More than the initial content of HFO-1234yf and CTFE in the total amount of HFO-1234yf and CTFE is lower than the content of HFO-1234yf and the total content of HFO-1234yf and CTFE in the initial mixture. The HFO-1234yf content in the total amount of the fraction and HFO-1234yf and CTFE is separated into a second fraction that is higher than the content of HFO-1234yf in the total amount of HFO-1234yf and CTFE in the initial mixture. HFO-1234yf having a reduced CTFE concentration from the second fraction Including that process.

第1の実施形態における蒸留の条件としては、HFO−1234yfとCTFE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CTFE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CTFE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CTFE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 the distillation conditions in the first embodiment, the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE is the content of HFO-1234yf in the total amount of HFO-1234yf and CTFE in the above initial mixture. The first fraction lower than the ratio and the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE is higher than the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE 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CTFE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CTFE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CTFE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CTFE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 CTFE. Is obtained as a distillate from the top of the distillation column, the content of which is lower than the content of HFO-1234yf in the total amount of HFO-1234yf and CTFE in the initial mixture. Further, the second fraction in which the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE is higher than the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE in the initial mixture is from the bottom of the column. Obtained as a bottomed liquid.

これは、上記の通り、圧力1.011×10PaにおけるHFO−1234yfとCTFEの共沸様組成物の沸点が41〜42.5℃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CTFE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CTFE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CTFE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CTFEの共沸組成物を得ることも可能である。 As described above, the boiling point of the azeotrope-like composition of HFO-1234yf and CTFE at a pressure of 1.011 × 10 6 Pa is 41 to 42.5 ° C., and the boiling point of HFO-1234yf is 43 ° C. It depends. The content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE 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 CTFE in the above initial mixture. The lower first fraction is usually obtained as a mixed composition comprising an azeotrope-like composition of HFO-1234yf and CTFE. It is also possible to finally obtain an azeotropic composition of HFO-1234yf and CTFE 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CTFE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CTFE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CTFE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 CTFE 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 CTFE in the initial mixture is The second fraction having a higher content ratio can be made to be a high purity HFO-1234yf having a lower CTFE 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CTFEからなる初期混合物であって、HFO−1234yfとCTFEの合計量中のCTFEの含有割合がモル比で51%を超える初期混合物を蒸留して、HFO−1234yfとCTFEの合計量中のCTFEの含有割合が、前記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFEの含有割合より低い第1留分と、HFO−1234yfとCTFEの合計量中のCTFEの含有割合が、前記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFE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CTFE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 CTFE, and the initial content of CTFE in the total amount of HFO-1234yf and CTFE exceeds 51% in terms of molar ratio. The first fraction obtained by distilling the mixture and having a CTFE content in the total amount of HFO-1234yf and CTFE lower than the content of CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture; The content of CTFE in the total amount of 1234yf and CTFE is separated into a second fraction higher than the content of CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture, and HFO-1234yf is separated from the second fraction. Obtaining CTFE having a reduced concentration.

第2の実施形態における蒸留の条件としては、HFO−1234yfとCTFEの合計量中のCTFEの含有割合が、上記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFEの含有割合より低い第1留分と、HFO−1234yfとCTFEの合計量中のCTFEの含有割合が、上記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFE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 CTFE content in the total amount of HFO-1234yf and CTFE is lower than the CTFE content in the total amount of HFO-1234yf and CTFE in the initial mixture. If the content of CTFE in the total amount of the fraction and HFO-1234yf and CTFE is higher than the content of CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture, the second fraction can be separated. 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CTFEの合計量中のCTFEの含有割合が、上記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFE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CTFEの合計量中のCTFEの含有割合が、上記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFE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 CTFE content in the total amount of HFO-1234yf and CTFE is included. A first fraction having a proportion lower than the content of CTFE in the total amount of HFO-1234yf and CTFE 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 CTFE in the total amount of HFO-1234yf and CTFE is higher than the content ratio of CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture is the bottoms from the column. As obtained.

これは、上記の通り、圧力1.011×10PaにおけるHFO−1234yfとCTFEの共沸様組成物の沸点が41〜42.5℃であり、またCTFEの沸点は45℃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CTFEの合計量中のCTFEの含有割合が、上記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFEの含有割合より低い第1留分は、通常、HFO−1234yfとCTFE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CTFE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 CTFE at a pressure of 1.011 × 10 6 Pa is 41 to 42.5 ° C., and the boiling point of CTFE is 45 ° C. as described above. . The first fraction obtained as a distillate from the top of the column, the content ratio of CTFE in the total amount of HFO-1234yf and CTFE is lower than the content ratio of CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture. Is usually obtained as a mixed composition comprising an azeotrope-like composition of HFO-1234yf and CTFE. It is also possible to finally obtain an azeotropic composition of HFO-1234yf and CTFE 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CTFEの合計量中のCTFEの含有割合が、上記初期混合物におけるHFO−1234yfとCTFEの合計量中のCTFE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CTFE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CTFEは、例えば、上記R40と、R22等の熱分解してFC: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FC: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CTFEは、さらに、PCTFE(CTFE重合体)、ECTFE(エチレン−CTFE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 CTFE in the total amount of HFO-1234yf and CTFE obtained as bottoms from the bottom of the column is higher than the content ratio of CTFE in the total amount of HFO-1234yf and CTFE in the initial mixture. The second fraction can be made high-purity CTFE with a lower HFO-1234yf concentration by further repeating distillation as necessary.
Thus, the high-purity CTFE obtained by the production method of the second embodiment of the present invention is, for example, R40, a fluorine-containing compound capable of generating F 2 C: by thermal decomposition, such as 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 CTFE is also useful as a raw material for fluororesins such as PCTFE (CTFE polymer) and ECTFE (ethylene-CTFE 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CTFEを表1に示す質量比で混合して得られる混合物1〜5を、500mLの圧力計付きオートクレーブに入れ、圧力が1.011×10Pa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1.011×10Pa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1〜5のサンプルを採取し、ガスクロマトグラフィーでHFO−1234yfとCTFE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 5 obtained by mixing HFO-1234yf and CTFE at a mass ratio shown in Table 1 are put into a 500 mL autoclave with a pressure gauge and gradually heated to 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 5 were taken from the gas phase and the liquid phase, HFO-1234yf and CTFE were analyzed by gas chromatography, and the composition ratio of the two 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1〜5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1〜5のようにオートクレーブに仕込む混合物中のCTFE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3の場合、気相および液相の組成は、HFO−1234yfが49モル%、CTFEが51モル%で一致した。このときの気相温度は41.7℃であり、比揮発度の値が1.00となった。CTFE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 5, respectively. When the ratio of CTFE in the mixture charged into the autoclave was gradually increased like the mixtures 1 to 5, the relative volatility value gradually increased as shown in Table 1. In the case of the mixture 3, the composition of the gas phase and the liquid phase was 49 mol% for HFO-1234yf and 51 mol% for CTFE. The gas phase temperature at this time was 41.7 ° C., and the value of relative volatility was 1.00. When the ratio of CTFE 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CTFEの組成を、上記同様にしてHFO−1234yfとCTFE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1.011×10Paの場合に、HFO−1234yfとCTFEの含有割合が、HFO−1234yf/CTFEで示されるモル比で23/77〜91/9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 CTFE 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 CTFE 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 composition ratio of HFO-1234yf and CTFE is 23/77 to 91/9 in a molar ratio represented by HFO-1234yf / CTFE. The volatility was 1.00 ± 0.10.

Figure 2013230996
Figure 2013230996

[実施例1]
初期混合物として、HFO−1234yfとCTFEからなる混合物であり、該混合物全量中HFO−1234yfを75モル%、CTFE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149g/hrの速度で留出液を抜き出し、塔底より151g/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 CTFE and containing 75 mol% HFO-1234yf and 25 mol% CTFE 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 extracted from the top of the column at a rate of 149 g / hr, and a bottom is extracted from the bottom of the column at a rate of 151 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CTFEの合計量中のHFO−1234yfの含有割合がモル比で49%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CTFE濃度が高くHFO−1234yf濃度が低い、HFO−1234yfとCTFEの共沸様組成物が得られ、塔底からは該初期混合物よりCTFE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 was performed using a mixture in which the content ratio of HFO-1234yf in the total amount of HFO-1234yf and CTFE was more than 49% in terms of molar ratio as the initial mixture, from the top, An azeotrope-like composition of HFO-1234yf and CTFE with a higher CTFE concentration and a lower HFO-1234yf concentration than the initial mixture is obtained, and a high purity HFO-1234yf is obtained from the bottom of the column with a lower CTFE concentration than the initial mixture. I understand that

[実施例2]
初期混合物として、HFO−1234yfとCTFEからなる混合物であり、該混合物全量中HFO−1234yfを20モル%、CTFEを80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123g/hrの速度で留出液を抜き出し、塔底より177g/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 CTFE and containing 20 mol% HFO-1234yf and 80 mol% CTFE 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 123 g / hr, and the bottoms is withdrawn from the bottom of the column at a rate of 177 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CTFEの合計量中のCTFEの含有割合がモル比で51%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CTFE濃度が低い、HFO−1234yfとCTFE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CTFE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 CTFE in the total amount of HFO-1234yf and CTFE exceeds 51% in terms of the molar ratio as the initial mixture, from the top of the mixture, It can be seen that an azeotrope-like composition of HFO-1234yf and CTFE having a high HFO-1234yf concentration and a low CTFE concentration is obtained, and CTFE having a high purity is obtained from the bottom of the column with a low HFO-1234yf concentration.

Figure 2013230996
Figure 2013230996

Claims (7)

2,3,3,3−テトラフルオロプロペンを49モル%、クロロトリフルオロエチレンを51モル%含有する共沸組成物。   An azeotropic composition containing 49 mol% 2,3,3,3-tetrafluoropropene and 51 mol% chlorotrifluoroethylene. 2,3,3,3−テトラフルオロプロペンを23〜91モル%、クロロトリフルオロエチレンを77〜9モル%含有する共沸様組成物。   An azeotrope-like composition containing 23-91 mol% 2,3,3,3-tetrafluoropropene and 77-9 mol% chlorotrifluoroethylene. 2,3,3,3−テトラフルオロプロペンとクロロトリフルオロエチレ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クロロトリフルオロエチレ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クロロトリフルオロエチレ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/クロロトリフルオロエチレン=49/51である混合組成物。   A mixed composition comprising 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, wherein the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is in the mixed composition 90 mol% or more, and the content ratio of 2,3,3,3-tetrafluoropropene to chlorotrifluoroethylene is 2,3,3,3-tetrafluoropropene / chlorotrifluoroethylene = 49 / in molar ratio. 51. A mixed composition which is 51. 2,3,3,3−テトラフルオロプロペンとクロロトリフルオロエチレ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クロロトリフルオロエチレ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クロロトリフルオロエチレ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/クロロトリフルオロエチレン=23/77〜91/9である混合組成物。   A mixed composition comprising 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, wherein the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is in the mixed composition 90 mol% or more, and the content ratio of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is 2,3,3,3-tetrafluoropropene / chlorotrifluoroethylene = 23 / in molar ratio. A mixed composition that is 77-91 / 9. 請求項1または2に記載の組成物を含む冷媒。   A refrigerant comprising the composition according to claim 1 or 2. 主として2,3,3,3−テトラフルオロプロペンとクロロトリフルオロエチレ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クロロトリフルオロエチレンの合計量中の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49%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クロロトリフルオロエチレンの合計量中の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クロロトリフルオロエチレンの合計量中の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クロロトリフルオロエチレンの合計量中の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クロロトリフルオロエチレンの合計量中の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留分からクロロトリフルオロエチレン濃度が低下した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 mainly consisting of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, wherein 2,3,3 in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene The initial mixture in which the content ratio of 3,3-tetrafluoropropene exceeds 49% by mole is distilled,
The content ratio of 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is 2,3,3,3-tetrafluoroethylene in the initial mixture. A first fraction lower than the content of 2,3,3,3-tetrafluoropropene in the total amount of fluoropropene and chlorotrifluoroethylene, and 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene Of 2,3,3,3-tetrafluoropropene in the total amount of 2,3,3,3-tetrafluoropropene and 2,3,3 in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene in the initial mixture. It was separated into a second fraction higher than the content of 3,3-tetrafluoropropene, and the chlorotrifluoroethylene concentration decreased from the second fraction. Comprising obtaining a 3-tetrafluoropropene, 2,3,3,3 method for producing tetrafluoropropene.
主として2,3,3,3−テトラフルオロプロペンとクロロトリフルオロエチレ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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレンの含有割合がモル比で51%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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレンの含有割合が、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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレ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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレンの含有割合が、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クロロトリフルオロエチレンの合計量中のクロロトリフルオロエチレ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クロロトリフルオロエチレンを得る工程を含む、クロロトリフルオロエチレンの製造方法。
Chlorotrifluoroethylene in an initial mixture mainly consisting of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene in a total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene The initial mixture having a molar content of more than 51% by distillation is distilled,
The content ratio of chlorotrifluoroethylene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene is 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene in the initial mixture. A first fraction lower than the content ratio of chlorotrifluoroethylene in the total amount of chlorotrifluoroethylene, and the content ratio of chlorotrifluoroethylene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, The initial mixture is separated into a second fraction higher than the content of chlorotrifluoroethylene in the total amount of 2,3,3,3-tetrafluoropropene and chlorotrifluoroethylene, and 2,3 from the second fraction. A step of obtaining chlorotrifluoroethylene having a reduced concentration of 1,3,3-tetrafluoropropene Method for producing chlorotrifluoroethylene.
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