WO2015045927A1 - Method for separating hexafluoropropene from fluorinated compound - Google Patents

Method for separating hexafluoropropene from fluorinated compound Download PDF

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WO2015045927A1
WO2015045927A1 PCT/JP2014/074313 JP2014074313W WO2015045927A1 WO 2015045927 A1 WO2015045927 A1 WO 2015045927A1 JP 2014074313 W JP2014074313 W JP 2014074313W WO 2015045927 A1 WO2015045927 A1 WO 2015045927A1
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composition
hfp
distillation
fluorine
containing compound
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PCT/JP2014/074313
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French (fr)
Japanese (ja)
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優 竹内
哲央 大塚
古田　昇二
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旭硝子株式会社
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Priority to JP2015539117A priority Critical patent/JPWO2015045927A1/en
Publication of WO2015045927A1 publication Critical patent/WO2015045927A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
    • C07C17/386—Separation; Purification; Stabilisation; Use of additives by distillation with auxiliary compounds

Definitions

  • the present invention relates to a method for separating hexafluoropropene (HFP), and relates to a method for separating HFP and a fluorine-containing compound having a boiling point close to that of HFP.
  • HFP hexafluoropropene
  • a fluorine-containing compound having a boiling point close to that of HFP a fluorine-containing compound having a boiling point close to that of HFP.
  • a fluorine-containing compound having a small influence on the ozone layer and having a small global warming potential has been demanded as a refrigerant.
  • Such a fluorine-containing compound is produced, for example, by a synthetic reaction involving thermal decomposition using a compound partially containing the molecular structure of the target substance as a raw material gas.
  • a synthetic reaction involving thermal decomposition using a compound partially containing the molecular structure of the target substance as a raw material gas.
  • various compounds similar in structure to the target substance are by-produced in addition to the target substance.
  • HFO-1234yf 2,3,3,3-tetrafluoropropene (HFO-1234yf), which has little impact on the ozone layer and has a low warming potential, is thermally decomposed using chlorodifluoromethane (R22) and chloromethane (R40) as raw materials. It is known that it is produced by a synthesis reaction involving the above (see, for example, Patent Document 1).
  • removal of by-products from the reaction product obtained is usually carried out by distillation using a difference in boiling point.
  • a compound having a boiling point close to that of HFO-1234yf such as hexafluoropropene (HFP) is generally used. Removal by distillation is difficult, and a method for efficiently removing these has been demanded.
  • HFP and R22 are known to form an azeotropic composition at a predetermined molar ratio.
  • a composition containing a plurality of compounds is distilled such that two specific compounds in the composition form an azeotropic composition or an azeotrope-like composition, and the two compounds are separated. Boiling distillation is generally performed. In azeotropic distillation, an azeotropic composition or an azeotrope-like composition is separated by taking advantage of the fact that the azeotropic composition has a lower boiling point than other compounds. (For example, refer to Patent Document 2).
  • HFP and R22 are known to azeotrope in these two component systems, for example, HFP can be obtained from the reaction product obtained by the thermal decomposition synthesis reaction of HFO-1234yf using this.
  • a multi-component system including a plurality of fluorine-containing compounds having a boiling point close to that of HFP each compound is an azeotropic composition even if it is intended to be separated as an azeotrope or azeotrope-like composition with other compounds in the reaction product. It is not known whether HFP can be separated, because no interaction is known about the interaction between each compound in the formation of.
  • the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for efficiently separating HFP and a fluorine-containing compound having a boiling point close to that of the HFP.
  • the present invention provides a method for separating HFP comprising the following steps (a) and (b) from a fluorine-containing compound having a boiling point of ⁇ 10 ° C. to + 15 ° C. of the boiling point of the HFP. (A) preparing a distillation composition comprising hexafluoropropene, a fluorine-containing compound having a boiling point of ⁇ 10 ° C. to + 15 ° C.
  • HFP and a fluorine-containing compound having a boiling point close to that of HFP can be efficiently separated.
  • the boiling point of the compound is a value at normal pressure (1.013 ⁇ 10 5 Pa).
  • the separation method of the present invention comprises HFP (boiling point ⁇ 29 ° C.) and a fluorine-containing compound having a boiling point of ⁇ 10 ° C. to + 15 ° C. of the HFP, that is, a fluorine-containing compound having a boiling point of ⁇ 39 to ⁇ 14 ° C. , A fluorine-containing compound (A)), and a distillation composition containing HFP, the above-mentioned fluorine-containing compound (A) and R22 (boiling point -41 ° C.) is prepared.
  • This is a method for efficiently separating HFP and fluorine-containing compound (A) by subjecting the composition to distillation in which a fraction containing the HFP and R22 azeotrope or azeotrope-like composition is formed. .
  • the inventors of the present invention incorporated R22 into an initial mixture containing HFP and a fluorine-containing compound (A) having a boiling point of ⁇ 10 ° C. to + 15 ° C. which is the boiling point of HFP to obtain a distillation composition. It has been found that subjecting the composition to distillation preferentially forms an azeotropic or azeotrope-like composition of HFP and R22 over a combination of other compounds. A specific range as will be described later by utilizing that the boiling point difference between the azeotropic composition of HFP and R22 and the fluorine-containing compound (A) is larger than the boiling point difference between HFP and the fluorine-containing compound (A).
  • the HFP and R22 azeotrope or azeotrope-like composition of the following composition could be selectively removed from the distillation composition.
  • the distillation composition is divided into a fraction containing an azeotropic or azeotrope-like composition of HFP and R22 (hereinafter also referred to as “first fraction”) and distillation.
  • the HFP is separated from the composition into fractions from which HFP has been separated (hereinafter also referred to as “second fraction”).
  • compounds other than fluorine-containing compounds such as R40 ( ⁇ 24 ° C.), N-chlorodimethylamine (Cl—) can be used as long as they have a boiling point of ⁇ 10 ° C. to + 15 ° C.
  • An azeotropic composition is a composition in which the gas phase generated by vaporization of the liquid phase has the same composition as the liquid phase to be vaporized, or the gas phase generated by liquefaction of the gas phase is liquefied. Defined as a composition having the same composition as the phase. Therefore, the azeotropic composition does not change in composition when repeated evaporation and condensation, and can be distilled and / or refluxed without changing the composition.
  • the composition of the azeotropic composition is determined as a composition in which the composition in the liquid phase and the composition in the gas phase are equal, that is, the relative volatility is 1.00. However, the composition of the azeotropic composition can vary with pressure.
  • the azeotropic composition of HFP and R22 is a composition having a molar ratio of 77/23 represented by R22 / HFP at normal pressure (1.013 ⁇ 10 5 Pa), and represented by R22 / HFP at a gauge pressure of 0.6 MPa.
  • the composition has a molar ratio of 87/13.
  • the azeotropic composition of HFP and R22 is such that the relative volatility represented by the following formula (1) is 1.00 at normal pressure.
  • the azeotropic composition of HFP and R22 has a boiling point of ⁇ 42.3 ° C. at normal pressure and a boiling point of 10.2 ° C. at a gauge pressure of 0.6 MPa.
  • a composition having a composition close to the azeotropic composition is an azeotrope-like composition exhibiting behavior close to azeotropic. That is, an azeotrope-like composition has a tendency not to fractionate when evaporated or agglomerated, and the composition of the gas phase produced by the vaporization of the liquid phase is different from the composition of the vaporized liquid phase or the gas phase.
  • the composition of the liquid phase produced by liquefaction of the phase is substantially the same as the composition of the gas phase to be liquefied.
  • an azeotrope-like composition can be distilled and / or refluxed with little compositional change.
  • the composition range of the azeotrope-like composition of HFP and R22 is a range in which the composition is distilled and / or refluxed with almost no change in composition under normal distillation conditions.
  • the composition range in which the composition is distilled and / or refluxed with little change in composition can be defined as a range in which the relative volatility at a predetermined pressure is 1.00 ⁇ ⁇ , for example.
  • the composition range of the azeotrope-like composition of HFP and R22 is a range in which the relative volatility is 1.00 ⁇ 0.20 at a predetermined pressure.
  • the composition range of the azeotrope-like composition of HFP and R22 having a relative volatility in the range of 1.00 ⁇ 0.20 at normal pressure is such that the content ratio as a molar ratio represented by R22 / HFP is 70/30. ⁇ 85/15.
  • the boiling point of the azeotrope-like composition of HFP and R22 in the above composition range is ⁇ 42.3 to ⁇ 42.2 ° C.
  • the composition range of the azeotrope-like composition of HFP and R22 having a relative volatility in the range of 1.00 ⁇ 0.20 at 0.6 MPa (gauge pressure) is the content ratio as a molar ratio represented by R22 / HFP. Is 75/25 to 98/2, and the boiling point of the azeotrope-like composition of HFP and R22 in the above composition range is 10.2 to 10.6 ° C. at 0.6 MPa (gauge pressure).
  • Table 1 shows the pressure and the composition range of the azeotrope-like composition by simulation using known thermodynamic characteristics and calculated thermodynamic characteristics.
  • the azeotrope-like composition can be handled almost the same as the azeotrope composition.
  • an azeotrope-like composition is described as including an azeotrope composition.
  • Step (a) in the present invention comprises a distillation composition comprising hexafluoropropene (HFP), a fluorine-containing compound having a boiling point of -10 to + 15 ° C., and chlorodifluoromethane (R22). It is a process to prepare.
  • HFP hexafluoropropene
  • R22 chlorodifluoromethane
  • the fluorine-containing compound (A) has a boiling point of HFP of ⁇ 10 ° C. to + 15 ° C., preferably ⁇ 8 ° C. to + 10 ° C., more preferably ⁇ 5 ° C. to + 8 ° C. Therefore, the fluorine-containing compound (A) in the separation method of the present invention has a boiling point of ⁇ 39 to ⁇ 14 ° C., preferably ⁇ 37 to ⁇ 19 ° C., more preferably ⁇ 34 to ⁇ 21 ° C.
  • the fluorine-containing compound (A) in the present invention is not particularly limited as long as the boiling point is a fluorine-containing compound having the above-described range, and one kind may be used alone, or two or more kinds may be mixed.
  • fluorine-containing compound (A) examples include chloropentafluoroethane (CFC-115), fluoroethane (HFC-161), octafluoropropane (PFC-218), 3,3-difluoropropene (HFO-1252zf), Dichlorodifluoromethane (CFC-12), 2,3,3,3-tetrafluoropropene (HFO-1234yf), chlorotrifluoroethylene (CTFE), 1,1,1,2-tetrafluoroethane (HFC-134a) 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethylene (Z) (HFO-1132 (Z)), 3,3,3-trifluoropropene (HFO-1243zf), 1, 1-difluoroethane (HFC-152a), 1-chloro-1-fluoroethane (HCFC-151a), 1,1,2,2-tetrafluoroethane (HFC-134
  • the fluorine-containing compound (A) preferably contains at least one selected from the group consisting of CTFE, HFO-1234yf, HFO-1243zf and HFO-1234ze (Z / E). It is particularly preferable that it contains HFO-1234yf because it has a small coefficient and is useful as a refrigerant.
  • the composition for distillation in the present invention contains HFP, the above-mentioned fluorine-containing compound (A) and R22.
  • the contents of HFP, fluorine-containing compound (A) and R22 in the distillation composition in the present invention are not particularly limited. In the present invention, if R22 is contained in the composition for distillation, HFP and the fluorine-containing compound (A) can be separated. Therefore, what is necessary is just to determine suitably content of R22 in the composition for distillation according to the desired purity of a 2nd fraction.
  • the ratio of the amount of the fluorine-containing compound (A) to the total amount of the composition for distillation is preferably 10 mol% or more, thereby improving the yield of the fluorine-containing compound (A).
  • the proportion of the fluorine-containing compound (A) contained in the distillation composition is more preferably 30 mol% or more.
  • the molar ratio indicated by R22 / HFP in the distillation composition is preferably equal to or higher than the lower limit of the molar ratio indicated by R22 / HFP of the azeotrope-like composition at a predetermined distillation pressure. It is more preferable that the molar ratio is not less than that shown by HFP. If the molar ratio indicated by R22 / HFP is not less than the lower limit of the molar ratio indicated by R22 / HFP of the azeotrope-like composition at the pressure, the azeotrope-like composition of HFP and R22 in a specific composition range can be efficiently produced. The HFP separation rate can be extremely increased. Moreover, if the molar ratio shown by R22 / HFP is more than the molar ratio shown by R22 / HFP of the azeotropic composition, HFP in the composition for distillation can be more efficiently separated in the first fraction. .
  • the amount of R22 relative to HFP in the distillation composition at normal pressure is preferably 2.3 or more, more preferably 3.3 or more, in a molar ratio represented by R22 / HFP. If the molar ratio represented by R22 / HFP is 2.3 or more, it becomes larger than the lower limit value of R22 / HFP (70 / 30 ⁇ 2.3) of the azeotrope-like composition at normal pressure, so a special temperature It is possible to efficiently separate an azeotrope-like composition of HFP and R22 in a specific composition range under distillation conditions that are usually performed without using pressure conditions, and extremely increase the HFP separation rate.
  • the amount of R22 to HFP in the distilled composition at 0.6 MPa is preferably 3 or more, more preferably 5 or more in terms of a molar ratio represented by R22 / HFP. More preferably, it is 7 or more.
  • the molar ratio represented by R22 / HFP when the molar ratio represented by R22 / HFP is increased, the amount of R22 in the second fraction increases, but as shown in Table 2, the boiling point of R22 and the fluorine-containing compound (A) is not so close. There is no problem because it can be easily separated by an ordinary distillation method.
  • the molar ratio represented by R22 / HFP in the distilled composition is preferably 100 or less, and more preferably 50 or less.
  • the reboiler load is increased by increasing the amount of the distillation composition itself, and therefore, it is preferably set to the upper limit or less.
  • the composition for distillation in the present invention can be prepared, for example, by adding a predetermined amount of R22 to an initial mixture containing HFP and a fluorine-containing compound (A).
  • the initial mixture contains HFP, the fluorine-containing compound (A), and R22, the initial mixture can be used as it is as a composition for distillation.
  • the initial mixture may contain only HFP and the fluorine-containing compound (A), or may contain HFP, the fluorine-containing compound (A) and R22.
  • HFP and the fluorine-containing compound (A) are included in the initial mixture and R22 is not included, R22 may be added.
  • the content of HFP in the initial mixture is measured, and the content of HFP is determined according to the content of HFP.
  • R22 can be added to the above-mentioned preferable amount to obtain a composition for distillation.
  • the fluorine-containing compound (A) and R22, the HFP content and the R22 content are measured, and the total amount of R22 contained in the initial mixture and R22 to be added is preferable as described above. It is good also as a composition for distillation by adding the quantity of R22 used as quantity.
  • the molar ratio represented by R22 / HFP in the initial mixture is not less than the upper limit, it is not necessary to adjust this to a preferred range.
  • the composition for distillation of the present invention is not necessarily formed only by HFP, the fluorine-containing compound (A) and R22, and HFP, the fluorine-containing compound (A) and R22 are within a range not impairing the effects of the present invention. Other compounds may be included.
  • the initial mixture in the separation method of the present invention is, for example, R40 and a fluorine-containing compound that can be thermally decomposed to generate F 2 C :, for example, R22, tetrafluoroethylene (TFE), octafluorocyclobutane. (RC318), CTFE, trifluoroethylene, hexafluoropropylene oxide (HFPO), etc.
  • a fluorine-containing compound that can be thermally decomposed to generate F 2 C :, for example, R22, tetrafluoroethylene (TFE), octafluorocyclobutane. (RC318), CTFE, trifluoroethylene, hexafluoropropylene oxide (HFPO), etc.
  • a reaction product obtained by a method for synthesizing a fluorine-containing compound (A) accompanied by thermal decomposition, by distillation or the like It can be obtained by fractionating a distillate comprising the raw material for the reaction and the produced fluorine-containing compound (A) or a distillate comprising the reaction product as a main component.
  • Examples of the fluorine-containing compound (A) contained in the initial mixture obtained by the above method include CFC-115, HFC-161, PFC-218, HFO-1252zf, CFC-12, HFO-1234yf, CTFE, HFC-134a, and HCFO.
  • the distillate obtained by the method for synthesizing the fluorine-containing compound (A) is used as an initial mixture for distillation in the separation method of the present invention, HFP, the fluorine-containing compound (A), and It is not necessary that components other than R22 are completely removed. That is, the distillate (initial mixture) may contain other compounds other than HFP, fluorine-containing compound (A) and R22 within a range not impairing the effects of the present invention.
  • R40 TFE, RC318, trifluoroethylene, heptafluoropropane, chloroethylene, 1,1-difluoroethylene (HFO-1132a), chlorotetrafluoroethane (HCFC-124), chlorofluoromethane (HCFC-31), difluoromethane ( HFC-32) and the like may be contained.
  • HFO-1132a 1,1-difluoroethylene
  • HCFC-124 chlorotetrafluoroethane
  • HCFC-31 chlorofluoromethane
  • HFC-32 difluoromethane
  • Process of this invention is a process of providing the said composition for distillation to the distillation in which the fraction containing the said HFP and said R22 azeotrope composition or an azeotrope-like composition is formed.
  • the first fraction containing the azeotrope-like composition of HFP and R22 is formed by distilling the distillation composition containing HFP, the fluorine-containing compound (A) and R22 in the above-described range. be able to.
  • the pressure is preferably set to 0 to 3 MPa as a gauge pressure. It is preferable to adjust the temperature appropriately within the range of ⁇ 42 to 71 ° C. as the tower top temperature depending on the set pressure. Distillation may be performed batchwise or continuously. The distillation is preferably performed so that the ratio of the amount of HFP in the fraction (first fraction) to the amount of HFP in the composition for distillation (HFP separation rate) is 75% or more, and 80% or more. More preferably, 90% or more is more preferable, and 95% or more is most preferable.
  • the ratio of the amount of the fluorine-containing compound (A) in the fraction (first fraction) to the amount of the fluorine-containing compound (A) in the distillation composition is 25% or less. 20% or less is more preferable, 10% or less is more preferable, and 5% or less is most preferable. Thereby, a higher purity fluorine-containing compound (A) can be obtained.
  • the column top temperature is set to be equal to or higher than the boiling point of the azeotrope-like composition at the distillation pressure, and the column bottom temperature is fluorinated. It is preferable to make it below the boiling point of a compound (A). This is mainly done by adjusting the tower top temperature. At this time, the reboiler load can be reduced by reducing the difference between the tower top temperature and the tower bottom temperature. In addition, the reboiler load can be reduced by setting the pressure so that the boiling point of the azeotrope-like composition is around room temperature, for example, approximately -15 to 50 ° C. Such pressure is preferably 0.2 to 2.0 MPa. What is necessary is just to set these temperature conditions and pressure conditions suitably according to the purity of the fluorine-containing compound (A) calculated
  • the step (b) includes a distillation column, a means for supplying a distillation composition, a means for taking out the distillate from the top of the distillation tower, and a means for taking out the bottom liquid from the bottom of the distillation tower. It can be performed using the distillation apparatus provided. In the said distillation apparatus, while obtaining a 1st fraction as a distillate, the 2nd fraction from which the HFP was substantially isolate
  • the boiling point of the azeotrope-like composition of HFP and R22 at normal pressure (1.013 ⁇ 10 5 Pa) is ⁇ 42.3 to ⁇ 42.2 ° C.
  • the fluorine-containing compound ( This is because the boiling point of A) is -39 to -14 ° C.
  • the second fraction is distilled by a usual method.
  • a higher purity fluorine-containing compound (A) can be obtained.
  • Examples 1 to 11 are examples, and example 12 is a comparative example.
  • the present invention is not limited to the following examples.
  • Examples 1 to 10 and Example 12 are results of performing a distillation simulation using known thermodynamic characteristics and calculated thermodynamic characteristics.
  • Example 1 As a composition for distillation, HFP was 8,264 ppm (molar conversion), R22, HFC-161, HFO-1252zf, HFO-1234yf, HFC-134a, HFO-1243zf, R40, HFC-152a, HFC-134, HFO Preparation of Distillation Composition 1 containing -1225zc, HFO-1225ye, and HFO-1234ze, each containing 100 moles of HFO-1234yf, 10 moles of R22, and 1 mole of other compounds per mole of HFP To do.
  • distillate 1 is taken out from the top of the tower and bottoms 1 is taken out from the bottom of the tower.
  • Table 3 shows the composition of distillation composition 1, distillate 1 and bottoms 1, the tower top temperature, and the tower bottom temperature.
  • the recovery rate indicates the ratio (percentage) of the molar amount of the compound contained in the distillate 1 or the bottoms 1 with respect to the molar amount of each compound contained in the composition 1 for distillation.
  • the reboiler load in this distillation is shown in the lower column of Table 3.
  • Example 1 an azeotropic or azeotrope-like composition of HFP and R22 is obtained as a distillate 1 from the top of the column, and a bottom 1 that essentially does not contain HFP is obtained from the bottom of the column. In Example 1, 98.5% of HFP in the composition 1 for distillation is separated in the distillate.
  • Example 2 to Example 10 The composition for distillation contains HFP, HFO-1234yf and R22, and 100 mol of HFO-1234yf and R22 / HFP in an amount shown in the following Tables 4 to 12 with respect to 1 mol of HFP.
  • Distillation composition 2 to distillation composition 10 are prepared and distilled using the same distillation apparatus as in Example 1 under the same conditions as in Example 1.
  • Example 2 Example 5, Example 6, and Example 7, the column top temperature was changed to 14.1 ° C., 16.3 ° C., 20.0 ° C., and 20.7 ° C. respectively in the conditions of Example 1 to Distill in the same way.
  • the distillates 2 to 10 and the bottoms 2 to 10 obtained in Examples 2 to 10 are recovered in the same manner as in Example 1. Tables 4 to 12 show these compositions and tower top / bottom temperature.
  • HFO-1234yf separation rate (mol%)
  • the amount of HFO-1234yf in the distillate with respect to the amount of HFO-1234yf in the distillate composition determined by the formula: HFO-1234yf mol amount in the distillate / HFO-1234yf mol amount in the distillate composition ⁇ 100 Means the percentage of [HFO-1234yf / (HFO-1234yf + HFP)] (mol%) MFO amount of HFO-1234yf / (molar amount of HFO-1234yf + molar amount of HFP) ⁇ 100, which means the ratio of the amount of HFO-1234yf to the total amount of HFO-1234yf and HFP in the bottoms.
  • HFO-1234yf / (HFO-1234yf + HFP) ⁇ 100 of the distillation composition in Examples 2 to 10 is 99.010 [mol%].
  • HFO-1234yf and HFP are separated with high accuracy.
  • a distillate mainly containing an azeotropic composition or an azeotrope-like composition of HFP and R22 is obtained as a distillate
  • HFO-1234yf from which HFP is separated is obtained as a distillate.
  • the recovery rate of HFP in the distillate improves as R22 / HFP increases.
  • the amount of HFO-1234yf relative to HFP in the bottoms is remarkably increased.
  • the larger R22 / HFP is, the more remarkable the effect is.
  • the HFP separation rate is slightly inferior to the other examples, but it can be seen that the reboiler load is small.
  • R22 and R40 (hereinafter referred to as source gas) each preheated to 500 ° C. were continuously introduced into the reactor in the electric furnace, and steam (water vapor) heated to 800 ° C. was further introduced into the reactor.
  • the temperature and pressure (gauge pressure) in the reactor were measured values, respectively, and the temperature was 770 ° C. and the pressure was 0.04 MPa.
  • the flow rate of the source gas (amount supplied per unit time) was controlled so that the residence time of the source gas in the reactor was 1 second, and the generated gas was taken out from the outlet of the reactor. Next, the gas taken out from the outlet of the reactor was cooled to 100 ° C.
  • Example 11 the obtained composition for distillation 11 is supplied to the bottom of a distillation column having 55 theoretical plates, and distillation by batch distillation is performed until the operating pressure becomes 0.9 MPa (gauge pressure) and the top temperature reaches 29 ° C. It was. R22 / HFP in Example 11 is 43.4. Distillation is conducted while extracting and collecting the distillate 11 at 1.37 g / min. After 1,830 minutes from the start of distillation, the extraction of the distillate 11 is stopped and the temperature at the bottom of the column is lowered to about room temperature. The remaining bottoms 11 was collected. During the distillation, the column bottom temperature was maintained at 37-40 ° C.
  • Example 11 Each composition of the distillate 11 and the bottoms 11 obtained in Example 11 was analyzed by gas chromatography. Table 13 shows the mass of the compound contained in the distillate 11 and the bottom 11. In Example 11, with regard to HFO-1225ye and HFO-1132, the E form and the Z form were analyzed separately.
  • Example 12 A composition 12 containing 100 moles of HFO-1234yf and 1 mole of HFP and no R22 is prepared with HFP and HFO-1234yf. This composition 12 is distilled under the same conditions as in Example 1 using the same distillation apparatus as in Example 1. The distillate 12 is recovered from the top of the column, and the bottom 12 is recovered from the bottom of the column in the same manner as in Example 1. Table 14 shows the distillation conditions of Example 12, the composition of the distillate 12 and the bottoms 12 obtained in Example 12, and the reboiler load. The HFO-1234yf / (HFO-1234yf + HFP) ⁇ 100 of the composition for distillation 12 in Example 12 is 99.010 [mol%].
  • HFP and the fluorine-containing compound (A) having a boiling point close to that of HFP can be efficiently separated.
  • HFP and a fluorine-containing compound having a boiling point close to that of HFP can be efficiently separated.

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Abstract

Provided is a method for separating HFP from a fluorinated compound having a boiling point that is close to the boiling point of HFP with high efficiency. A method for separating HFP from a fluorinated compound having a boiling point falling within the range from a temperature that is lower by 10˚C than the boiling point of HFP to a temperature that is higher by 15˚C than the boiling point of HFP, said method being characterized by comprising the steps of: (a) providing a composition to be distilled, which comprises HFP, the fluorinated compound having a boiling point falling within the range from a temperature that is lower by 10˚C than the boiling point of HFP to a temperature that is higher by 15˚C than the boiling point of HFP, and R22; and (b) subjecting the composition to be distilled to a distillation procedure for producing a fraction containing an azeotropic or azeotrope-like composition produced from HFP and R22.

Description

ヘキサフルオロプロペンと含フッ素化合物の分離方法Method for separating hexafluoropropene and fluorine-containing compound
　本発明はヘキサフルオロプロペン（ＨＦＰ）の分離方法に係り、ＨＦＰと当該ＨＦＰと沸点が近い含フッ素化合物を分離する方法に関する。
　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し、必要に応じて化合物名に代えてその略称を用いる。 The present invention relates to a method for separating hexafluoropropene (HFP), and relates to a method for separating HFP and a fluorine-containing compound having a boiling point close to that of HFP.
In the present specification, for a halogenated hydrocarbon, the abbreviation of the compound is described in parentheses after the compound name, and the abbreviation is used instead of the compound name as necessary.
　近年、冷媒としてオゾン層への影響が少なく、温暖化係数の小さい含フッ素化合物が求められている。このような含フッ素化合物は、例えば、目的物質の分子構造を部分的に含む化合物を原料ガスとして、熱分解を伴う合成反応により製造されている。しかしながら、熱分解を伴う合成反応では、目的物質以外に、目的物質と構造の類似した多種の化合物が副生することも知られている。 In recent years, a fluorine-containing compound having a small influence on the ozone layer and having a small global warming potential has been demanded as a refrigerant. Such a fluorine-containing compound is produced, for example, by a synthetic reaction involving thermal decomposition using a compound partially containing the molecular structure of the target substance as a raw material gas. However, it is also known that, in a synthesis reaction involving thermal decomposition, various compounds similar in structure to the target substance are by-produced in addition to the target substance.
　例えば、オゾン層への影響が少なくかつ温暖化係数の小さい２，３，３，３－テトラフルオロプロペン（ＨＦＯ－１２３４ｙｆ）は、クロロジフルオロメタン（Ｒ２２）とクロロメタン（Ｒ４０）を原料として熱分解を伴う合成反応で製造することが知られている（例えば、特許文献１参照。）。ここで、通常、得られる反応生成物からの副生物の除去は蒸留により沸点差を利用して行われるが、ヘキサフルオロプロペン（ＨＦＰ）等のＨＦＯ－１２３４ｙｆと沸点の近い化合物は、一般的な蒸留での除去は困難であり、これらを効率よく除去する方法が求められていた。 For example, 2,3,3,3-tetrafluoropropene (HFO-1234yf), which has little impact on the ozone layer and has a low warming potential, is thermally decomposed using chlorodifluoromethane (R22) and chloromethane (R40) as raw materials. It is known that it is produced by a synthesis reaction involving the above (see, for example, Patent Document 1). Here, removal of by-products from the reaction product obtained is usually carried out by distillation using a difference in boiling point. However, a compound having a boiling point close to that of HFO-1234yf such as hexafluoropropene (HFP) is generally used. Removal by distillation is difficult, and a method for efficiently removing these has been demanded.
　一方、ＨＦＰおよびＲ２２は、所定のモル比で共沸組成物を形成することが知られている。また、複数の化合物を含む組成物を、当該組成物中の特定の２種の化合物が共沸組成物または共沸様組成物を形成するように蒸留し、当該２種の化合物を分離する共沸蒸留が一般的に行われている。共沸蒸留では、共沸組成物が、他の化合物よりも低い沸点をもつことを利用して共沸組成物または共沸様組成物を分離する。（例えば、特許文献２参照。）。 On the other hand, HFP and R22 are known to form an azeotropic composition at a predetermined molar ratio. In addition, a composition containing a plurality of compounds is distilled such that two specific compounds in the composition form an azeotropic composition or an azeotrope-like composition, and the two compounds are separated. Boiling distillation is generally performed. In azeotropic distillation, an azeotropic composition or an azeotrope-like composition is separated by taking advantage of the fact that the azeotropic composition has a lower boiling point than other compounds. (For example, refer to Patent Document 2).
　ここで、ＨＦＰおよびＲ２２はこれらの２成分系で共沸することが知られているものの、例えば、これを利用して上記ＨＦＯ－１２３４ｙｆの熱分解合成反応で得られた反応生成物からＨＦＰを反応生成物中の他の化合物との共沸組成物または共沸様組成物として分離しようとしても、ＨＦＰと沸点が近い含フッ素化合物を複数種含む多成分系では、各化合物が共沸組成物を形成する場合の各化合物間の相互作用について何ら知られておらず、ＨＦＰを分離できるかどうかは明らかではなかった。さらに、このような多成分系では、２種の化合物のみならず３種以上の化合物が共沸組成物または共沸様組成物を形成することもあるため、共沸組成物または共沸様組成物を形成する可能性のある化合物の組合せやその態様は限りなく多く、これら全てについて詳細に分析するのは非常に困難であった。 Here, although HFP and R22 are known to azeotrope in these two component systems, for example, HFP can be obtained from the reaction product obtained by the thermal decomposition synthesis reaction of HFO-1234yf using this. In a multi-component system including a plurality of fluorine-containing compounds having a boiling point close to that of HFP, each compound is an azeotropic composition even if it is intended to be separated as an azeotrope or azeotrope-like composition with other compounds in the reaction product. It is not known whether HFP can be separated, because no interaction is known about the interaction between each compound in the formation of. Further, in such a multi-component system, not only two compounds but also three or more compounds may form an azeotropic composition or an azeotrope-like composition. There are an unlimited number of combinations and forms of compounds that can form products, and it has been very difficult to analyze all of them in detail.
日本特許第５２０１２８４号公報Japanese Patent No. 5201284 日本特公昭３９－１９６２４号公報Japanese Patent Publication No. 39-19624
　本発明は上記した課題を解決するためになされたものであって、ＨＦＰと当該ＨＦＰと沸点が近い含フッ素化合物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 to solve the above-described problems, and an object of the present invention is to provide a method for efficiently separating HFP and a fluorine-containing compound having a boiling point close to that of the HFP.
　本発明は、以下の（ａ）工程および（ｂ）工程を含むＨＦＰと当該ＨＦＰの沸点の－１０℃から＋１５℃の沸点を有する含フッ素化合物との分離方法を提供する。
　（ａ）ヘキサフルオロプロペン、該ヘキサフルオロプロペンの沸点の－１０℃から＋１５℃の沸点を有する含フッ素化合物およびクロロジフルオロメタンを含む蒸留用組成物を準備する工程と、
　（ｂ）前記ヘキサフルオロプロペンおよび前記クロロジフルオロメタンの共沸組成物または共沸様組成物を含む留分が形成される蒸留に前記蒸留用組成物を供する工程。 The present invention provides a method for separating HFP comprising the following steps (a) and (b) from a fluorine-containing compound having a boiling point of −10 ° C. to + 15 ° C. of the boiling point of the HFP.
(A) preparing a distillation composition comprising hexafluoropropene, a fluorine-containing compound having a boiling point of −10 ° C. to + 15 ° C. of the boiling point of the hexafluoropropene, and chlorodifluoromethane;
(B) A step of subjecting the composition for distillation to distillation in which a fraction containing an azeotropic composition or an azeotrope-like composition of the hexafluoropropene and the chlorodifluoromethane is formed.
　本発明の分離方法によれば、ＨＦＰと当該ＨＦＰと沸点が近い含フッ素化合物を効率よく分離することができる。 According to the separation method of the present invention, HFP and a fluorine-containing compound having a boiling point close to that of HFP can be efficiently separated.
　以下、本発明の実施の形態を説明する。本発明は以下の実施形態に限定されるものではない。なお、本明細書において、特に断りのない限り、化合物の沸点は常圧（１．０１３×１０５Ｐａ）での値である。 Embodiments of the present invention will be described below. The present invention is not limited to the following embodiments. In the present specification, unless otherwise specified, the boiling point of the compound is a value at normal pressure (1.013 × 10 5 Pa).
　本発明の分離方法は、ＨＦＰ（沸点－２９℃）と当該ＨＦＰの沸点の－１０℃から＋１５℃の沸点を有する含フッ素化合物、すなわち、沸点が－３９～－１４℃の含フッ素化合物（以下、含フッ素化合物（Ａ）ともいう。）とを分離する方法であって、ＨＦＰ、上記含フッ素化合物（Ａ）およびＲ２２（沸点－４１℃）を含む蒸留用組成物を準備し、当該蒸留用組成物を、前記ＨＦＰおよび前記Ｒ２２の共沸組成物または共沸様組成物を含む留分が形成される蒸留に供することで、ＨＦＰと含フッ素化合物（Ａ）を効率よく分離する方法である。 The separation method of the present invention comprises HFP (boiling point −29 ° C.) and a fluorine-containing compound having a boiling point of −10 ° C. to + 15 ° C. of the HFP, that is, a fluorine-containing compound having a boiling point of −39 to −14 ° C. , A fluorine-containing compound (A)), and a distillation composition containing HFP, the above-mentioned fluorine-containing compound (A) and R22 (boiling point -41 ° C.) is prepared. This is a method for efficiently separating HFP and fluorine-containing compound (A) by subjecting the composition to distillation in which a fraction containing the HFP and R22 azeotrope or azeotrope-like composition is formed. .
　上述したように、Ｒ２２、ＨＦＰおよびＨＦＰと沸点の近接した含フッ素化合物を含む多成分系では、共沸組成物の形成に際しての各化合物間の相互作用について何ら知られておらず、共沸組成物または共沸様組成物の形成態様の全てについて詳細に分析するのは非常に困難であった。 As described above, in the multi-component system containing R22, HFP, and a fluorine-containing compound having a boiling point close to that of HFP, no interaction is known between the compounds at the time of forming the azeotropic composition. It was very difficult to analyze in detail about all the formation aspects of the product or the azeotrope-like composition.
　このようななか、本発明者らは、ＨＦＰおよびＨＦＰの沸点の－１０℃から＋１５℃の沸点を有する含フッ素化合物（Ａ）を含む初期混合物にＲ２２を含有させて蒸留用組成物とし、当該蒸留用組成物を蒸留に供することで、他の化合物の組合せよりもＨＦＰおよびＲ２２の共沸組成物または共沸様組成物を優先的に形成させることを見出した。そして、ＨＦＰおよびＲ２２の共沸組成物と含フッ素化合物（Ａ）との沸点差がＨＦＰと含フッ素化合物（Ａ）との沸点差よりも大きくなることを利用して、後述するような特定範囲の組成のＨＦＰおよびＲ２２の共沸組成物または共沸様組成物を蒸留用組成物から選択的に取り出すことを可能とした。これにより、本発明の分離方法は、蒸留用組成物を、ＨＦＰおよびＲ２２の共沸組成物または共沸様組成物を含む留分(以下、「第１留分」ともいう。)と蒸留用組成物からＨＦＰの分離された留分（以下、「第２留分」ともいう。）とに分離するものである。 Under these circumstances, the inventors of the present invention incorporated R22 into an initial mixture containing HFP and a fluorine-containing compound (A) having a boiling point of −10 ° C. to + 15 ° C. which is the boiling point of HFP to obtain a distillation composition. It has been found that subjecting the composition to distillation preferentially forms an azeotropic or azeotrope-like composition of HFP and R22 over a combination of other compounds. A specific range as will be described later by utilizing that the boiling point difference between the azeotropic composition of HFP and R22 and the fluorine-containing compound (A) is larger than the boiling point difference between HFP and the fluorine-containing compound (A). The HFP and R22 azeotrope or azeotrope-like composition of the following composition could be selectively removed from the distillation composition. Thus, in the separation method of the present invention, the distillation composition is divided into a fraction containing an azeotropic or azeotrope-like composition of HFP and R22 (hereinafter also referred to as “first fraction”) and distillation. The HFP is separated from the composition into fractions from which HFP has been separated (hereinafter also referred to as “second fraction”).
　なお、本発明によれば、ＨＦＰの沸点の－１０℃から＋１５℃の沸点を有する化合物であれば、含フッ素化合物以外の化合物、例えばＲ４０（－２４℃）、Ｎ－クロロジメチルアミン（Ｃｌ－Ｎ－[ＣＨ３]２、－３９℃）、ブロモアセチレン（Ｂｒ－Ｃ≡Ｃ－Ｈ、－３６℃）、プロパジエン（ＣＨ２＝Ｃ＝ＣＨ２、－３５℃）、塩素（Ｃｌ２、－３４℃）、ジアゾメタン（ＣＨ２－Ｎ２、－２３℃）、ジメチルシラン（ＣＨ３－ＳｉＨ２－ＣＨ３、－２２℃）、ジシアン（ＮＣ－ＣＮ、－２１℃）、エチニルメチルエーテル（ＣＨ≡Ｃ－Ｏ－ＣＨ３、－１７℃）、塩化ビニル（ＣＨ２＝ＣＨＣｌ、－１４℃）、アンモニア（ＮＨ３、－３３℃）、シクロプロパン（－（ＣＨ２－ＣＨ２－ＣＨ２）－、－３３℃）、クロロアセチレン（Ｃｌ－Ｃ≡Ｃ－Ｈ、－３０℃）、ジメチルエーテル（ＣＨ３－Ｏ－ＣＨ３、－２４℃）、ホルムアルデヒド（Ｈ－Ｃ（Ｏ）－Ｈ、－１９℃）等、であっても、ＨＦＰとの分離が可能である。なお、括弧内の温度は各化合物の沸点を示す。以下、ＨＦＰおよびＲ２２の共沸組成物または共沸様組成物について説明する。 According to the present invention, compounds other than fluorine-containing compounds such as R40 (−24 ° C.), N-chlorodimethylamine (Cl—) can be used as long as they have a boiling point of −10 ° C. to + 15 ° C. N- [CH 3 ] 2 , −39 ° C.), bromoacetylene (Br—C≡C—H, −36 ° C.), propadiene (CH 2 ═C═CH 2 , −35 ° C.), chlorine (Cl 2 , − 34 ° C.), diazomethane (CH 2 —N 2 , −23 ° C.), dimethylsilane (CH 3 —SiH 2 —CH 3 , −22 ° C.), dicyan (NC-CN, −21 ° C.), ethynyl methyl ether (CH ≡C—O—CH 3 , −17 ° C.), vinyl chloride (CH 2 ═CHCl, −14 ° C.), ammonia (NH 3 , −33 ° C.), cyclopropane (— (CH 2 —CH 2 —CH 2 )) -, -33 ° C), chloro Acetylene (Cl—C≡C—H, −30 ° C.), dimethyl ether (CH 3 —O—CH 3 , −24 ° C.), formaldehyde (HC (O) —H, −19 ° C.), etc. Also, separation from HFP is possible. The temperature in parentheses indicates the boiling point of each compound. Hereinafter, the azeotropic or azeotrope-like composition of HFP and R22 will be described.
　共沸組成物は、液相の気化により生成される気相が、気化される液相と同一の組成を有する組成物、または、気相の液化により生成される液相が、液化される気相と同一の組成を有する組成物として定義される。よって、共沸組成物は、蒸発、凝縮を繰り返した場合の組成の変動がなく、組成の変化を伴わずに蒸留および／または還流されうる。共沸組成物の組成は、液相における組成と気相における組成が等しい、すなわち比揮発度が１．００となる組成として求められる。ただし、共沸組成物の組成は圧力により変化しうる。 An azeotropic composition is a composition in which the gas phase generated by vaporization of the liquid phase has the same composition as the liquid phase to be vaporized, or the gas phase generated by liquefaction of the gas phase is liquefied. Defined as a composition having the same composition as the phase. Therefore, the azeotropic composition does not change in composition when repeated evaporation and condensation, and can be distilled and / or refluxed without changing the composition. The composition of the azeotropic composition is determined as a composition in which the composition in the liquid phase and the composition in the gas phase are equal, that is, the relative volatility is 1.00. However, the composition of the azeotropic composition can vary with pressure.
　ＨＦＰおよびＲ２２の共沸組成物は、常圧（１．０１３×１０５Ｐａ）においてＲ２２／ＨＦＰで示されるモル比が７７／２３の組成物、ゲージ圧０．６ＭＰａにおいてＲ２２／ＨＦＰで示されるモル比が８７／１３の組成物である。このＨＦＰおよびＲ２２の共沸組成は、常圧において、下記式（１）で示される比揮発度が１．００となる組成である。また、ＨＦＰおよびＲ２２の共沸組成物は、常圧での沸点が－４２．３℃、ゲージ圧０．６ＭＰａでの沸点が１０．２℃である。 The azeotropic composition of HFP and R22 is a composition having a molar ratio of 77/23 represented by R22 / HFP at normal pressure (1.013 × 10 5 Pa), and represented by R22 / HFP at a gauge pressure of 0.6 MPa. The composition has a molar ratio of 87/13. The azeotropic composition of HFP and R22 is such that the relative volatility represented by the following formula (1) is 1.00 at normal pressure. The azeotropic composition of HFP and R22 has a boiling point of −42.3 ° C. at normal pressure and a boiling point of 10.2 ° C. at a gauge pressure of 0.6 MPa.
（ＨＦＰに対するＲ２２の比揮発度の式）
　比揮発度＝（気相部におけるＲ２２のモル％／気相部におけるＨＦＰのモル％）／（液相部におけるＲ２２のモル％／液相部におけるＨＦＰのモル％）　　…（１） (R22 relative volatility formula for HFP)
Specific volatility = (mol% of R22 in gas phase part / mol% of HFP in gas phase part) / (mol% of R22 in liquid phase part / mol% of HFP in liquid phase part) (1)
　また、一般的に、共沸組成を形成する組成物において、共沸組成に近似する組成の組成物は共沸に近い挙動を示す共沸様組成物とされる。すなわち、共沸様組成物は、蒸発または凝集されたときに分画されない傾向を有し、液相の気化により生成される気相の組成が、気化される液相の組成と、または、気相の液化により生成される液相の組成が、液化される気相の組成と略同一である。したがって、共沸様組成物は組成の変化をほとんど伴わずに蒸留および／または還流されうる。 In general, in a composition forming an azeotropic composition, a composition having a composition close to the azeotropic composition is an azeotrope-like composition exhibiting behavior close to azeotropic. That is, an azeotrope-like composition has a tendency not to fractionate when evaporated or agglomerated, and the composition of the gas phase produced by the vaporization of the liquid phase is different from the composition of the vaporized liquid phase or the gas phase. The composition of the liquid phase produced by liquefaction of the phase is substantially the same as the composition of the gas phase to be liquefied. Thus, an azeotrope-like composition can be distilled and / or refluxed with little compositional change.
　ＨＦＰおよびＲ２２の共沸様組成物の組成範囲としては、具体的には、通常の蒸留条件において、該組成物が組成の変化をほとんど伴わずに蒸留および／または還流される範囲であることが好ましい。組成物が組成の変化をほとんど伴わずに蒸留および／または還流される組成範囲は、例えば、所定の圧力における比揮発度が１．００±αとなる範囲として規定できる。 Specifically, the composition range of the azeotrope-like composition of HFP and R22 is a range in which the composition is distilled and / or refluxed with almost no change in composition under normal distillation conditions. preferable. The composition range in which the composition is distilled and / or refluxed with little change in composition can be defined as a range in which the relative volatility at a predetermined pressure is 1.00 ± α, for example.
　ＨＦＰおよびＲ２２の共沸様組成物の組成範囲としては、具体的には、所定の圧力において比揮発度が１．００±０．２０となる範囲である。なお、常圧での比揮発度が１．００±０．２０の範囲のＨＦＰおよびＲ２２の共沸様組成物の組成範囲は、Ｒ２２／ＨＦＰで示されるモル比としての含有割合が７０／３０～８５／１５である。また、常圧において、上記組成範囲のＨＦＰおよびＲ２２の共沸様組成物の沸点は－４２．３～－４２．２℃である。また０．６ＭＰａ(ゲージ圧)での比揮発度が１．００±０．２０の範囲のＨＦＰおよびＲ２２の共沸様組成物の組成範囲は、Ｒ２２／ＨＦＰで示されるモル比としての含有割合が７５／２５～９８／２であり、０．６ＭＰａ(ゲージ圧)において、上記組成範囲のＨＦＰおよびＲ２２の共沸様組成物の沸点は１０．２～１０．６℃である。表１に、既知の熱力学特性・計算熱力学特性を用いたシミュレーションによる圧力と共沸様組成物の組成範囲を示す。なお、共沸様組成物は、共沸組成物とほぼ同等に取り扱える。以下、共沸様組成物は共沸組成物を含むものとして記載する。 Specifically, the composition range of the azeotrope-like composition of HFP and R22 is a range in which the relative volatility is 1.00 ± 0.20 at a predetermined pressure. The composition range of the azeotrope-like composition of HFP and R22 having a relative volatility in the range of 1.00 ± 0.20 at normal pressure is such that the content ratio as a molar ratio represented by R22 / HFP is 70/30. ~ 85/15. At normal pressure, the boiling point of the azeotrope-like composition of HFP and R22 in the above composition range is −42.3 to −42.2 ° C. The composition range of the azeotrope-like composition of HFP and R22 having a relative volatility in the range of 1.00 ± 0.20 at 0.6 MPa (gauge pressure) is the content ratio as a molar ratio represented by R22 / HFP. Is 75/25 to 98/2, and the boiling point of the azeotrope-like composition of HFP and R22 in the above composition range is 10.2 to 10.6 ° C. at 0.6 MPa (gauge pressure). Table 1 shows the pressure and the composition range of the azeotrope-like composition by simulation using known thermodynamic characteristics and calculated thermodynamic characteristics. The azeotrope-like composition can be handled almost the same as the azeotrope composition. Hereinafter, an azeotrope-like composition is described as including an azeotrope composition.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　以下、本発明の分離方法における各工程について説明する。
　（ａ）工程
　本発明における（ａ）工程は、ヘキサフルオロプロペン（ＨＦＰ）、該ＨＦＰの沸点－１０～＋１５℃の沸点を有する含フッ素化合物およびクロロジフルオロメタン（Ｒ２２）を含む蒸留用組成物を準備する工程である。 Hereinafter, each step in the separation method of the present invention will be described.
Step (a) Step (a) in the present invention comprises a distillation composition comprising hexafluoropropene (HFP), a fluorine-containing compound having a boiling point of -10 to + 15 ° C., and chlorodifluoromethane (R22). It is a process to prepare.
　含フッ素化合物（Ａ）は、ＨＦＰの沸点の－１０℃から＋１５℃、好ましくは－８℃から＋１０℃、より好ましくは－５℃から＋８℃の沸点を有する。したがって、本発明の分離方法における含フッ素化合物（Ａ）は、沸点が－３９～－１４℃、好ましくは－３７～－１９℃、より好ましくは－３４～－２１℃である。本発明における含フッ素化合物（Ａ）は、沸点が上記した範囲の含フッ素化合物であれば特に限定されず、１種単独であってもよく、２種以上が混合されていてもよい。 The fluorine-containing compound (A) has a boiling point of HFP of −10 ° C. to + 15 ° C., preferably −8 ° C. to + 10 ° C., more preferably −5 ° C. to + 8 ° C. Therefore, the fluorine-containing compound (A) in the separation method of the present invention has a boiling point of −39 to −14 ° C., preferably −37 to −19 ° C., more preferably −34 to −21 ° C. The fluorine-containing compound (A) in the present invention is not particularly limited as long as the boiling point is a fluorine-containing compound having the above-described range, and one kind may be used alone, or two or more kinds may be mixed.
　含フッ素化合物（Ａ）としては、例えば、クロロペンタフルオロエタン（ＣＦＣ－１１５）、フルオロエタン（ＨＦＣ－１６１）、オクタフルオロプロパン（ＰＦＣ－２１８）、３，３－ジフルオロプロペン（ＨＦＯ－１２５２ｚｆ）、ジクロロジフルオロメタン（ＣＦＣ－１２）、２，３，３，３－テトラフルオロプロペン（ＨＦＯ－１２３４ｙｆ）、クロロトリフルオロエチレン（ＣＴＦＥ）、１，１，１，２－テトラフルオロエタン（ＨＦＣ－１３４ａ）、１－クロロ－１－フルオロエチレン（ＨＣＦＯ－１１３１ａ）、１，２－ジフルオロエチレン（Ｚ）（ＨＦＯ－１１３２（Ｚ））、３，３，３－トリフルオロプロペン（ＨＦＯ－１２４３ｚｆ）、１，１－ジフルオロエタン（ＨＦＣ－１５２ａ）、１－クロロ－１－フルオロエタン（ＨＣＦＣ－１５１ａ）、１，１，２，２－テトラフルオロエタン（ＨＦＣ－１３４）、１，１，３，３，３－ペンタフルオロプロペン（ＨＦＯ－１２２５ｚｃ）、１，１，２，３，３－ペンタフルオロプロペン（ＨＦＯ－１２２５ｙｃ）、１，２，３，３，３－ペンタフルオロプロペン（Ｚ）（ＨＦＯ－１２２５ｙｅ（Ｚ））、１，２，３，３，３－ペンタフルオロプロペン（Ｅ）（ＨＦＯ－１２２５ｙｅ（Ｅ））、１，３，３，３－テトラフルオロプロペン（Ｚ）（ＨＦＯ－１２３４ｚｅ（Ｚ））、１，３，３，３－テトラフルオロプロペン（Ｅ）（ＨＦＯ－１２３４ｚｅ（Ｅ））、１，１，１，２，２－ペンタフルオロプロパン（ＨＦＣ－２４５ｃｂ）、１－フルオロプロペン（Ｚ）（ＨＦＣ－１２６１ｚｅ（Ｚ））、１－フルオロプロペン（Ｅ）（ＨＦＣ－１２６１ｚｅ（Ｅ））、２－フルオロプロペン（ＨＦＣ－１２６１ｙｆ）、ヘキサフルオロアセトン、１，１，１，２，３，３，３－ヘプタフルオロプロパン（ＨＦＣ－２２７ｅａ）、１，１，１，２，２，３，３－ヘプタフルオロプロパン（ＨＦＣ－２２７ｃａ）、ヘキサフルオロプロピレンオキサイド（ＨＦＰＯ）、１－クロロ－１，２－ジフルオロエチレン（ＨＣＦＯ－１１２２ａ）および１－クロロ－２，２－ジフルオロエチレン（ＨＣＦＯ－１１２２）からなる群から選ばれる少なくとも１種を含むものが挙げられる。上記した化合物の沸点を表２に示す。 Examples of the fluorine-containing compound (A) include chloropentafluoroethane (CFC-115), fluoroethane (HFC-161), octafluoropropane (PFC-218), 3,3-difluoropropene (HFO-1252zf), Dichlorodifluoromethane (CFC-12), 2,3,3,3-tetrafluoropropene (HFO-1234yf), chlorotrifluoroethylene (CTFE), 1,1,1,2-tetrafluoroethane (HFC-134a) 1-chloro-1-fluoroethylene (HCFO-1131a), 1,2-difluoroethylene (Z) (HFO-1132 (Z)), 3,3,3-trifluoropropene (HFO-1243zf), 1, 1-difluoroethane (HFC-152a), 1-chloro-1-fluoroethane (HCFC-151a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,3,3,3-pentafluoropropene (HFO-1225zc), 1,1,2,3 , 3-Pentafluoropropene (HFO-1225yc), 1,2,3,3,3-pentafluoropropene (Z) (HFO-1225ye (Z)), 1,2,3,3,3-pentafluoropropene (E) (HFO-1225ye (E)), 1,3,3,3-tetrafluoropropene (Z) (HFO-1234ze (Z)), 1,3,3,3-tetrafluoropropene (E) ( HFO-1234ze (E)), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 1-fluoropropene (Z) (HFC-1261ze (Z)), 1-fluoro Propene (E) (HFC-1261ze (E)), 2-fluoropropene (HFC-1261yf), hexafluoroacetone, 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca), hexafluoropropylene oxide (HFPO), 1-chloro-1,2-difluoroethylene (HCFO-1122a) and 1-chloro And at least one selected from the group consisting of -2,2-difluoroethylene (HCFO-1122). Table 2 shows the boiling points of the above-mentioned compounds.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　これらのなかでも、含フッ素化合物（Ａ）としては、ＣＴＦＥ、ＨＦＯ－１２３４ｙｆ、ＨＦＯ－１２４３ｚｆおよびＨＦＯ－１２３４ｚｅ（Ｚ／Ｅ）からなる群から選ばれる１種以上を含むものであることが好ましく、温暖化係数が小さく、冷媒として有用であることから、ＨＦＯ－１２３４ｙｆを含むものであることが特に好ましい。 Among these, the fluorine-containing compound (A) preferably contains at least one selected from the group consisting of CTFE, HFO-1234yf, HFO-1243zf and HFO-1234ze (Z / E). It is particularly preferable that it contains HFO-1234yf because it has a small coefficient and is useful as a refrigerant.
　なお、含フッ素化合物（Ａ）において、化合物の後ろに（Ｚ）または（Ｅ）等の表記があるものは、幾何異性体のＺ体またはＥ体であることを示す。また、表２において、幾何異性体を有する化合物についてＺ体とＥ体に沸点の差がない場合は、化合物の後ろに（Ｚ／Ｅ）と表示した。また、ＨＣＦＯ－１１２２ａ（ＥｏｒＺ）については、ＨＣＦＯ－１１２２ａ（Ｅ）、ＨＣＦＯ－１１２２ａ（Ｚ）のうち低沸点の異性体を示すが、その構造異性体は不明であるため化合物の後ろに（Ｅ or Ｚ）と表記した。 In the fluorine-containing compound (A), those having the notation such as (Z) or (E) after the compound indicate that they are Z isomers or E isomers of geometric isomers. In Table 2, when there is no difference in boiling point between the Z-form and the E-form for a compound having a geometric isomer, (Z / E) is displayed after the compound. HCFO-1122a (EorZ) is a low-boiling isomer among HCFO-1122a (E) and HCFO-1122a (Z), but the structural isomer is unknown, and therefore (E or Z).
　本発明における蒸留用組成物はＨＦＰ、上記した含フッ素化合物（Ａ）およびＲ２２を含む。本発明における蒸留用組成物中のＨＦＰ、含フッ素化合物（Ａ）およびＲ２２の含有量は特に限定されない。本発明においては、蒸留用組成物にＲ２２が含まれていれば、ＨＦＰと含フッ素化合物（Ａ）を分離することができる。そのため、蒸留用組成物中のＲ２２の含有量は、第２留分の所望の純度に応じて適宜決定すればよい。 The composition for distillation in the present invention contains HFP, the above-mentioned fluorine-containing compound (A) and R22. The contents of HFP, fluorine-containing compound (A) and R22 in the distillation composition in the present invention are not particularly limited. In the present invention, if R22 is contained in the composition for distillation, HFP and the fluorine-containing compound (A) can be separated. Therefore, what is necessary is just to determine suitably content of R22 in the composition for distillation according to the desired purity of a 2nd fraction.
　蒸留用組成物の全量に対する含フッ素化合物（Ａ）の量の割合は、１０モル％以上であることが好ましく、これにより、含フッ素化合物（Ａ）の収量が向上する。蒸留用組成物に含まれる含フッ素化合物（Ａ）の割合は、さらに好ましくは３０モル％以上である。 The ratio of the amount of the fluorine-containing compound (A) to the total amount of the composition for distillation is preferably 10 mol% or more, thereby improving the yield of the fluorine-containing compound (A). The proportion of the fluorine-containing compound (A) contained in the distillation composition is more preferably 30 mol% or more.
　蒸留組成物中のＲ２２／ＨＦＰで示されるモル比は、所定の蒸留圧力における共沸様組成物のＲ２２／ＨＦＰで示されるモル比の下限以上であることが好ましく、共沸組成物のＲ２２／ＨＦＰで示されるモル比以上であることがより好ましい。Ｒ２２／ＨＦＰで示されるモル比が当該圧力における共沸様組成物のＲ２２／ＨＦＰで示されるモル比の下限以上であれば、特定の組成範囲のＨＦＰおよびＲ２２の共沸様組成物を効率よく分離し、ＨＦＰ分離率を極めて大きくすることができる。また、Ｒ２２／ＨＦＰで示されるモル比が共沸組成物のＲ２２／ＨＦＰで示されるモル比以上であれば、蒸留用組成物中のＨＦＰを第１留分中により効率よく分離することができる。 The molar ratio indicated by R22 / HFP in the distillation composition is preferably equal to or higher than the lower limit of the molar ratio indicated by R22 / HFP of the azeotrope-like composition at a predetermined distillation pressure. It is more preferable that the molar ratio is not less than that shown by HFP. If the molar ratio indicated by R22 / HFP is not less than the lower limit of the molar ratio indicated by R22 / HFP of the azeotrope-like composition at the pressure, the azeotrope-like composition of HFP and R22 in a specific composition range can be efficiently produced. The HFP separation rate can be extremely increased. Moreover, if the molar ratio shown by R22 / HFP is more than the molar ratio shown by R22 / HFP of the azeotropic composition, HFP in the composition for distillation can be more efficiently separated in the first fraction. .
　そのため、常圧における蒸留組成物中のＨＦＰに対するＲ２２の量は、Ｒ２２／ＨＦＰで示されるモル比で、２．３以上であることが好ましく、３．３以上であることがより好ましい。Ｒ２２／ＨＦＰで示されるモル比が２．３以上であれば、常圧における共沸様組成物のＲ２２／ＨＦＰの下限値（７０/３０≒２．３）よりも大きくなるので、特別な温度や圧力条件を用いずに通常行われる蒸留条件で、特定の組成範囲のＨＦＰおよびＲ２２の共沸様組成物を効率よく分離し、ＨＦＰ分離率を極めて大きくすることができる。 Therefore, the amount of R22 relative to HFP in the distillation composition at normal pressure is preferably 2.3 or more, more preferably 3.3 or more, in a molar ratio represented by R22 / HFP. If the molar ratio represented by R22 / HFP is 2.3 or more, it becomes larger than the lower limit value of R22 / HFP (70 / 30≈2.3) of the azeotrope-like composition at normal pressure, so a special temperature It is possible to efficiently separate an azeotrope-like composition of HFP and R22 in a specific composition range under distillation conditions that are usually performed without using pressure conditions, and extremely increase the HFP separation rate.
　また、０．６ＭＰａ(ゲージ圧)における蒸留組成物中のＨＦＰに対するＲ２２の量は、Ｒ２２／ＨＦＰで示されるモル比で３以上であることが好ましく、５以上であることがより好ましく、６．７以上であることがさらに好ましい。 Further, the amount of R22 to HFP in the distilled composition at 0.6 MPa (gauge pressure) is preferably 3 or more, more preferably 5 or more in terms of a molar ratio represented by R22 / HFP. More preferably, it is 7 or more.
　一方、Ｒ２２／ＨＦＰで示されるモル比を大きくすると、第２留分中のＲ２２の量は増加するが、表２に示す通り、Ｒ２２と含フッ素化合物（Ａ）とは、沸点がさほど近くなく通常の蒸留方法で容易に分離できるため問題とならない。ただし、添加するＲ２２の量が多くなり過ぎないという観点からは、蒸留組成物中のＲ２２／ＨＦＰで示されるモル比は１００以下であることが好ましく、５０以下であることがより好ましい。後述するように初期混合物にＲ２２を添加する場合には、蒸留用組成物自体の量が増加することでリボイラー負荷が大きくなることから、上記上限以下とすることが好ましい。また、蒸留用組成物のＲ２２／ＨＦＰで示されるモル比の上限をこのようにすることで、第２留分中のＲ２２と含フッ素化合物（Ａ）を分離するために必要なエネルギーを小さくできるため、工業的に有利である。 On the other hand, when the molar ratio represented by R22 / HFP is increased, the amount of R22 in the second fraction increases, but as shown in Table 2, the boiling point of R22 and the fluorine-containing compound (A) is not so close. There is no problem because it can be easily separated by an ordinary distillation method. However, from the viewpoint that the amount of R22 to be added does not increase excessively, the molar ratio represented by R22 / HFP in the distilled composition is preferably 100 or less, and more preferably 50 or less. As will be described later, when R22 is added to the initial mixture, the reboiler load is increased by increasing the amount of the distillation composition itself, and therefore, it is preferably set to the upper limit or less. Moreover, energy required in order to isolate | separate R22 and a fluorine-containing compound (A) in a 2nd fraction can be made small by making the upper limit of the molar ratio shown by R22 / HFP of a composition for distillation in this way. Therefore, it is industrially advantageous.
　本発明における蒸留用組成物は例えば、ＨＦＰと含フッ素化合物（Ａ）を含有する初期混合物にＲ２２を所定の量添加することで準備することができる。初期混合物がＨＦＰ、含フッ素化合物（Ａ）およびＲ２２を含有する場合には、初期混合物をそのまま蒸留用組成物として用いることができる。 The composition for distillation in the present invention can be prepared, for example, by adding a predetermined amount of R22 to an initial mixture containing HFP and a fluorine-containing compound (A). When the initial mixture contains HFP, the fluorine-containing compound (A), and R22, the initial mixture can be used as it is as a composition for distillation.
　初期混合物はＨＦＰと含フッ素化合物（Ａ）のみを含有していてもよく、ＨＦＰ、含フッ素化合物（Ａ）およびＲ２２を含有していてもよい。初期混合物中にＨＦＰおよび含フッ素化合物（Ａ）が含まれＲ２２が含まれない場合には、Ｒ２２を添加すればよく、例えば初期混合物中のＨＦＰの含有量を測定し、ＨＦＰの含有量に応じてＲ２２を上記した好ましい量添加して蒸留用組成物とすることができる。 The initial mixture may contain only HFP and the fluorine-containing compound (A), or may contain HFP, the fluorine-containing compound (A) and R22. When HFP and the fluorine-containing compound (A) are included in the initial mixture and R22 is not included, R22 may be added. For example, the content of HFP in the initial mixture is measured, and the content of HFP is determined according to the content of HFP. Thus, R22 can be added to the above-mentioned preferable amount to obtain a composition for distillation.
　初期混合物がＨＦＰ、含フッ素化合物（Ａ）およびＲ２２を含有する場合には、ＨＦＰの含有量およびＲ２２の含有量を測定し、初期混合物に含まれるＲ２２と添加するＲ２２の合計量が上記した好ましい量となる量のＲ２２を添加して蒸留用組成物としてもよい。ただし、初期混合物におけるＲ２２／ＨＦＰで示されるモル比が上限以上である場合にこれを好ましい範囲に調整する必要はない。なお、本発明の蒸留用組成物は必ずしもＨＦＰ、含フッ素化合物（Ａ）およびＲ２２のみで形成されている必要はなく、本発明の効果を損なわない範囲でＨＦＰ、含フッ素化合物（Ａ）およびＲ２２以外の化合物を含んでいてもよい。 When the initial mixture contains HFP, the fluorine-containing compound (A) and R22, the HFP content and the R22 content are measured, and the total amount of R22 contained in the initial mixture and R22 to be added is preferable as described above. It is good also as a composition for distillation by adding the quantity of R22 used as quantity. However, when the molar ratio represented by R22 / HFP in the initial mixture is not less than the upper limit, it is not necessary to adjust this to a preferred range. In addition, the composition for distillation of the present invention is not necessarily formed only by HFP, the fluorine-containing compound (A) and R22, and HFP, the fluorine-containing compound (A) and R22 are within a range not impairing the effects of the present invention. Other compounds may be included.
　本発明の分離方法における初期混合物は、具体的には、例えば、Ｒ４０と、熱分解してＦ２Ｃ：を発生しうる含フッ素化合物、例えば、Ｒ２２、テトラフルオロエチレン（ＴＦＥ）、オクタフルオロシクロブタン（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）等、を原料とする、熱分解を伴う含フッ素化合物（Ａ）の合成方法により得られる反応生成物から、蒸留等により、未反応の原料および生成した含フッ素化合物（Ａ）からなる留出物または該反応生成物を主成分とする留出物を分取することで得ることができる。 Specifically, the initial mixture in the separation method of the present invention is, for example, R40 and a fluorine-containing compound that can be thermally decomposed to generate F 2 C :, for example, R22, tetrafluoroethylene (TFE), octafluorocyclobutane. (RC318), CTFE, trifluoroethylene, hexafluoropropylene oxide (HFPO), etc. as raw materials, from a reaction product obtained by a method for synthesizing a fluorine-containing compound (A) accompanied by thermal decomposition, by distillation or the like, It can be obtained by fractionating a distillate comprising the raw material for the reaction and the produced fluorine-containing compound (A) or a distillate comprising the reaction product as a main component.
　上記方法で得られる初期混合物に含まれる含フッ素化合物（Ａ）としては、ＣＦＣ－１１５、ＨＦＣ－１６１、ＰＦＣ－２１８、ＨＦＯ－１２５２ｚｆ、ＣＦＣ－１２、ＨＦＯ－１２３４ｙｆ、ＣＴＦＥ、ＨＦＣ－１３４ａ、ＨＣＦＯ－１１３１ａ、ＨＦＯ－１１３２（Ｚ）、ＨＦＯ－１２４３ｚｆ、ＨＦＣ－１５２ａ、ＨＣＦＣ－１５１ａ、ＨＦＣ－１３４、ＨＦＯ－１２２５ｚｃ、ＨＦＯ－１２２５ｙｃ、ＨＦＯ－１２２５ｙｅ（Ｚ／Ｅ）、ＨＦＯ－１２３４ｚｅ（Ｚ／Ｅ）、ＨＦＣ－２４５ｃｂ、ＨＦＣ－１２６１ｚｅ（Ｚ／Ｅ）、ＨＦＣ－１２６１ｙｆ、ＨＦＣ－２２７ｅａ、ＨＦＣ－２２７ｃａ、ＨＦＰＯ、ＨＣＦＯ－１１２２ａ（ＥｏｒＺ）、およびＨＣＦＯ－１１２２が挙げられる。 Examples of the fluorine-containing compound (A) contained in the initial mixture obtained by the above method include CFC-115, HFC-161, PFC-218, HFO-1252zf, CFC-12, HFO-1234yf, CTFE, HFC-134a, and HCFO. -1131a, HFO-1132 (Z), HFO-1243zf, HFC-152a, HCFC-151a, HFC-134, HFO-1225zc, HFO-1225yc, HFO-1225ye (Z / E), HFO-1234ze (Z / E ), HFC-245cb, HFC-1261ze (Z / E), HFC-1261yf, HFC-227ea, HFC-227ca, HFPO, HCFO-1122a (EorZ), and HCFO-1122.
　なお、上記含フッ素化合物（Ａ）の合成方法により得られる上記留出物を、本発明の分離方法において、蒸留に供する初期混合物として用いる場合には、必ずしもＨＦＰ、上記含フッ素化合物（Ａ）およびＲ２２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、該留出物（初期混合物）は、ＨＦＰ、含フッ素化合物（Ａ）およびＲ２２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、Ｒ４０、ＴＦＥ、ＲＣ３１８、トリフルオロエチレン、ヘプタフルオロプロパン、クロロエチレン、１，１－ジフルオロエチレン（ＨＦＯ－１１３２ａ）、クロロテトラフルオロエタン（ＨＣＦＣ－１２４）、クロロフルオロメタン（ＨＣＦＣ－３１）、ジフルオロメタン（ＨＦＣ－３２）等を含有していてもよい。なお、初期混合物がＨＦＰ、含フッ素化合物（Ａ）およびＲ２２以外のその他の化合物を含有している場合でも、初期混合物が上記したような量でＲ２２を含有すれば本発明の効果を得ることができる。 When the distillate obtained by the method for synthesizing the fluorine-containing compound (A) is used as an initial mixture for distillation in the separation method of the present invention, HFP, the fluorine-containing compound (A), and It is not necessary that components other than R22 are completely removed. That is, the distillate (initial mixture) may contain other compounds other than HFP, fluorine-containing compound (A) and R22 within a range not impairing the effects of the present invention. Specifically, R40 , TFE, RC318, trifluoroethylene, heptafluoropropane, chloroethylene, 1,1-difluoroethylene (HFO-1132a), chlorotetrafluoroethane (HCFC-124), chlorofluoromethane (HCFC-31), difluoromethane ( HFC-32) and the like may be contained. Even when the initial mixture contains HFP, the fluorine-containing compound (A), and other compounds other than R22, the effects of the present invention can be obtained if the initial mixture contains R22 in the amount as described above. it can.
　（ｂ）工程
　本発明の（ｂ）工程は、前記ＨＦＰおよび前記Ｒ２２の共沸組成物または共沸様組成物を含む留分が形成される蒸留に前記蒸留用組成物を供する工程である。（ｂ）工程において、ＨＦＰ、含フッ素化合物（Ａ）およびＲ２２を上記した範囲で含む蒸留用組成物を蒸留することで、ＨＦＰおよびＲ２２の共沸様組成物を含む第１留分を形成させることができる。 (B) Process (b) Process of this invention is a process of providing the said composition for distillation to the distillation in which the fraction containing the said HFP and said R22 azeotrope composition or an azeotrope-like composition is formed. In the step (b), the first fraction containing the azeotrope-like composition of HFP and R22 is formed by distilling the distillation composition containing HFP, the fluorine-containing compound (A) and R22 in the above-described range. be able to.
　蒸留条件としては、圧力をゲージ圧で０～３ＭＰａとすることが好ましい。温度は設定圧力により、塔頂温度として－４２～７１℃の範囲で適宜調整することが好ましい。蒸留はバッチ式で行われても、連続式で行われてもよい。蒸留は、蒸留用組成物におけるＨＦＰの量に対する留分（第１留分）中のＨＦＰの量の割合（ＨＦＰの分離率）が７５％以上となるように行うことが好ましく、８０％以上がより好ましく、９０％以上がさらに好ましく、９５％以上が最も好ましい。また、蒸留用組成物における含フッ素化合物（Ａ）の量に対する留分（第１留分）中の含フッ素化合物（Ａ）の量の割合が２５％以下となるように蒸留を行うことが好ましく、２０％以下がより好ましく、１０％以下がさらに好ましく、５％以下が最も好ましい。これにより、より高純度の含フッ素化合物（Ａ）を得ることができる。 As distillation conditions, the pressure is preferably set to 0 to 3 MPa as a gauge pressure. It is preferable to adjust the temperature appropriately within the range of −42 to 71 ° C. as the tower top temperature depending on the set pressure. Distillation may be performed batchwise or continuously. The distillation is preferably performed so that the ratio of the amount of HFP in the fraction (first fraction) to the amount of HFP in the composition for distillation (HFP separation rate) is 75% or more, and 80% or more. More preferably, 90% or more is more preferable, and 95% or more is most preferable. Moreover, it is preferable to perform distillation so that the ratio of the amount of the fluorine-containing compound (A) in the fraction (first fraction) to the amount of the fluorine-containing compound (A) in the distillation composition is 25% or less. 20% or less is more preferable, 10% or less is more preferable, and 5% or less is most preferable. Thereby, a higher purity fluorine-containing compound (A) can be obtained.
　上記条件を満足させるためには、例えば、塔頂から共沸様組成物を留出液として取り出す場合、塔頂温度を蒸留圧力における共沸様組成物の沸点以上とし、塔底温度を含フッ素化合物（Ａ）の沸点以下とすることが好ましい。これは、主として塔頂温度を調整することで行われる。この際、塔頂温度と塔底温度の差を小さくすることでリボイラー負荷を低減することができる。また、圧力を共沸様組成物の沸点が常温近傍、例えばおおむね－１５～５０℃となるように設定することでリボイラー負荷を低減することができる。このような圧力としては、０．２～２．０ＭＰａであることが好ましい。これら温度条件、圧力条件は求められる含フッ素化合物（Ａ）の純度に応じて適宜設定すればよい。 In order to satisfy the above conditions, for example, when an azeotrope-like composition is taken out from the top of the column as a distillate, the column top temperature is set to be equal to or higher than the boiling point of the azeotrope-like composition at the distillation pressure, and the column bottom temperature is fluorinated. It is preferable to make it below the boiling point of a compound (A). This is mainly done by adjusting the tower top temperature. At this time, the reboiler load can be reduced by reducing the difference between the tower top temperature and the tower bottom temperature. In addition, the reboiler load can be reduced by setting the pressure so that the boiling point of the azeotrope-like composition is around room temperature, for example, approximately -15 to 50 ° C. Such pressure is preferably 0.2 to 2.0 MPa. What is necessary is just to set these temperature conditions and pressure conditions suitably according to the purity of the fluorine-containing compound (A) calculated | required.
　（ｂ）工程は、蒸留塔と、蒸留用組成物を供給する手段と、当該蒸留塔の塔頂から留出液を取り出す手段と、当該蒸留塔の塔底から缶出液を取り出す手段とを備えた蒸留装置を用いて行うことができる。当該蒸留装置では、留出液として第１留分を得るとともに、缶出液として蒸留用組成物からＨＦＰの実質的に分離された第２留分を得ることができる。これは、上記の通り、常圧（１．０１３×１０５Ｐａ）でのＨＦＰおよびＲ２２の共沸様組成物の沸点が－４２．３～－４２．２℃であり、また含フッ素化合物（Ａ）の沸点が－３９～－１４℃であることによる。 The step (b) includes a distillation column, a means for supplying a distillation composition, a means for taking out the distillate from the top of the distillation tower, and a means for taking out the bottom liquid from the bottom of the distillation tower. It can be performed using the distillation apparatus provided. In the said distillation apparatus, while obtaining a 1st fraction as a distillate, the 2nd fraction from which the HFP was substantially isolate | separated from the composition for distillation as a bottoms can be obtained. As described above, the boiling point of the azeotrope-like composition of HFP and R22 at normal pressure (1.013 × 10 5 Pa) is −42.3 to −42.2 ° C., and the fluorine-containing compound ( This is because the boiling point of A) is -39 to -14 ° C.
　なお、例えば上記蒸留用組成物を準備する工程においてＲ２２を上記した好ましい量以上とし、Ｒ２２の含まれる第２留分を得た場合には、当該第２留分を通常の方法で蒸留することでより高純度の含フッ素化合物（Ａ）を得ることができる。 In addition, for example, in the step of preparing the composition for distillation, when R22 is set to the above preferable amount or more and the second fraction containing R22 is obtained, the second fraction is distilled by a usual method. Thus, a higher purity fluorine-containing compound (A) can be obtained.
　次に、実施例を用いて本発明をより詳細に説明する。例１～例１１は実施例であり、例１２は比較例である。本発明は以下の実施例に限定されない。なお、例１～例１０、及び例１２は、既知の熱力学特性・計算熱力学特性を用いて、蒸留シミュレーションを行った結果である。 Next, the present invention will be described in more detail using examples. Examples 1 to 11 are examples, and example 12 is a comparative example. The present invention is not limited to the following examples. Examples 1 to 10 and Example 12 are results of performing a distillation simulation using known thermodynamic characteristics and calculated thermodynamic characteristics.
（例１）
　蒸留用組成物として、ＨＦＰを８，２６４ｐｐｍ（モル換算）と、Ｒ２２、ＨＦＣ－１６１、ＨＦＯ－１２５２ｚｆ、ＨＦＯ－１２３４ｙｆ、ＨＦＣ－１３４ａ、ＨＦＯ－１２４３ｚｆ、Ｒ４０、ＨＦＣ－１５２ａ、ＨＦＣ－１３４、ＨＦＯ－１２２５ｚｃ、ＨＦＯ－１２２５ｙｅ、ＨＦＯ－１２３４ｚｅを含み、ＨＦＰの１モルに対してそれぞれＨＦＯ－１２３４ｙｆを１００モル、Ｒ２２を１０モル、その他の化合物を１モルとなる量の蒸留用組成物１を調製する。（Ｒ２２／ＨＦＰ＝１０）この蒸留用組成物１を、ＨＦＰの供給速度が０．１ｍｏｌ／ｈとなるように、段数１００段の蒸留塔の塔頂から８０段目に供給し、運転圧力０．６ＭＰａ(ゲージ圧)、塔頂温度１０．２℃、塔底温度２６．５℃で連続的に蒸留を行う。このとき、還流液は蒸留塔の最上段に供給する。 (Example 1)
As a composition for distillation, HFP was 8,264 ppm (molar conversion), R22, HFC-161, HFO-1252zf, HFO-1234yf, HFC-134a, HFO-1243zf, R40, HFC-152a, HFC-134, HFO Preparation of Distillation Composition 1 containing -1225zc, HFO-1225ye, and HFO-1234ze, each containing 100 moles of HFO-1234yf, 10 moles of R22, and 1 mole of other compounds per mole of HFP To do. (R22 / HFP = 10) This distillation composition 1 was supplied to the 80th stage from the top of the distillation tower having 100 stages so that the HFP supply rate was 0.1 mol / h, and the operating pressure was 0. Distillation is continuously performed at a pressure of 0.6 MPa (gauge pressure), a column top temperature of 10.2 ° C, and a column bottom temperature of 26.5 ° C. At this time, the reflux liquid is supplied to the uppermost stage of the distillation column.
　また、塔頂より留出液１を、塔底より缶出液１を取り出す。蒸留用組成物１、留出液１、缶出液１の組成、塔頂温度及び塔底温度を表３に示す。表３において回収率は、蒸留用組成物１に含まれる各化合物のモル量に対する、留出液１または缶出液１に含まれる当該化合物のモル量の割合（百分率）を示している。また、この蒸留におけるリボイラー負荷を表３の下欄に示す。 Also, distillate 1 is taken out from the top of the tower and bottoms 1 is taken out from the bottom of the tower. Table 3 shows the composition of distillation composition 1, distillate 1 and bottoms 1, the tower top temperature, and the tower bottom temperature. In Table 3, the recovery rate indicates the ratio (percentage) of the molar amount of the compound contained in the distillate 1 or the bottoms 1 with respect to the molar amount of each compound contained in the composition 1 for distillation. The reboiler load in this distillation is shown in the lower column of Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　例１では、塔頂から留出液１としてＨＦＰおよびＲ２２の共沸組成物または共沸様組成物が得られ、塔底から本質的にＨＦＰを含有しない缶出液１が得られる。なお、例１では、留出液中に蒸留用組成物１中のＨＦＰの９８．５％が分離される。 In Example 1, an azeotropic or azeotrope-like composition of HFP and R22 is obtained as a distillate 1 from the top of the column, and a bottom 1 that essentially does not contain HFP is obtained from the bottom of the column. In Example 1, 98.5% of HFP in the composition 1 for distillation is separated in the distillate.
（例２～例１０）
　蒸留用組成物として、ＨＦＰ、ＨＦＯ－１２３４ｙｆおよびＲ２２を含み、ＨＦＰの１モルに対して、ＨＦＯ－１２３４ｙｆを１００モル、Ｒ２２をそれぞれＲ２２／ＨＦＰを下記表４～表１２で示される量で含む蒸留用組成物２～蒸留用組成物１０を調製し、例１と同様の蒸留装置を用いて例１と同様の条件で蒸留を行う。例２、例５、例６、例７では、例1の条件のうち、塔頂温度をそれぞれ１４．１℃、１６．３℃、２０．０℃、２０．７℃に変更して例１と同様に蒸留を行う。例２～例１０で得られた留出液２～例１０、缶出液２～例１０について例１と同様に回収する。これらの組成及び、塔頂・塔底温度を表４～表１２に示す。 (Example 2 to Example 10)
The composition for distillation contains HFP, HFO-1234yf and R22, and 100 mol of HFO-1234yf and R22 / HFP in an amount shown in the following Tables 4 to 12 with respect to 1 mol of HFP. Distillation composition 2 to distillation composition 10 are prepared and distilled using the same distillation apparatus as in Example 1 under the same conditions as in Example 1. In Example 2, Example 5, Example 6, and Example 7, the column top temperature was changed to 14.1 ° C., 16.3 ° C., 20.0 ° C., and 20.7 ° C. respectively in the conditions of Example 1 to Distill in the same way. The distillates 2 to 10 and the bottoms 2 to 10 obtained in Examples 2 to 10 are recovered in the same manner as in Example 1. Tables 4 to 12 show these compositions and tower top / bottom temperature.
　また、各例における、留出液中のＨＦＰ分離率（モル％）及びＨＦＯ－１２３４ｙｆ分離率（モル％）、缶出液中のＨＦＯ－１２３４ｙｆ／（ＨＦＯ－１２３４ｙｆ＋ＨＦＰ）（モル％）をそれぞれ求めた。これらの結果及び各例におけるリボイラー負荷を各表の下欄に示す。なお、上記値はそれぞれ次のことを意味するものである。 Further, in each example, the HFP separation rate (mol%) and HFO-1234yf separation rate (mol%) in the distillate, and HFO-1234yf / (HFO-1234yf + HFP) (mol%) in the bottoms are obtained. It was. These results and the reboiler load in each example are shown in the lower column of each table. The above values mean the following.
　［ＨＦＰ分離率（モル％）］
　留出液中のＨＦＰモル量／蒸留用組成物中のＨＦＰモル量×１００で求められ、蒸留用組成物中のＨＦＰの量に対する留出液中のＨＦＰの量の割合を意味する。
　［ＨＦＯ－１２３４ｙｆ分離率（モル％）］
　留出液中のＨＦＯ－１２３４ｙｆモル量／蒸留用組成物中のＨＦＯ－１２３４ｙｆモル量×１００で求められ、蒸留用組成物中のＨＦＯ－１２３４ｙｆの量に対する留出液中のＨＦＯ－１２３４ｙｆの量の割合を意味する。
　［ＨＦＯ－１２３４ｙｆ／（ＨＦＯ－１２３４ｙｆ＋ＨＦＰ）］(モル％)
　ＨＦＯ－１２３４ｙｆのモル量／（ＨＦＯ－１２３４ｙｆのモル量＋ＨＦＰのモル量）×１００で求められ、缶出液中のＨＦＯ－１２３４ｙｆとＨＦＰの合計量に対するＨＦＯ－１２３４ｙｆの量の割合を意味する。 [HFP separation rate (mol%)]
MFP molar amount in the distillate / HFP molar amount in the composition for distillation × 100, which means the ratio of the amount of HFP in the distillate to the amount of HFP in the composition for distillation.
[HFO-1234yf separation rate (mol%)]
The amount of HFO-1234yf in the distillate with respect to the amount of HFO-1234yf in the distillate composition determined by the formula: HFO-1234yf mol amount in the distillate / HFO-1234yf mol amount in the distillate composition × 100 Means the percentage of
[HFO-1234yf / (HFO-1234yf + HFP)] (mol%)
MFO amount of HFO-1234yf / (molar amount of HFO-1234yf + molar amount of HFP) × 100, which means the ratio of the amount of HFO-1234yf to the total amount of HFO-1234yf and HFP in the bottoms.
　なお、例２～例１０における蒸留用組成物のＨＦＯ－１２３４ｙｆ／（ＨＦＯ－１２３４ｙｆ＋ＨＦＰ）×１００はいずれも９９．０１０［モル％］である。 Note that the HFO-1234yf / (HFO-1234yf + HFP) × 100 of the distillation composition in Examples 2 to 10 is 99.010 [mol%].
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
　例２～例１０では、ＨＦＯ－１２３４ｙｆとＨＦＰとが高精度で分離される。その結果、留出液としてＨＦＰおよびＲ２２の共沸組成物または共沸様組成物を主として含む留分が得られ、缶出液としてＨＦＰの分離されたＨＦＯ－１２３４ｙｆが得られる。このとき、Ｒ２２／ＨＦＰが大きいほど留出液へのＨＦＰの回収率が向上する。また、例２～例１０では、缶出液中のＨＦＰに対するＨＦＯ－１２３４ｙｆの量が著しく増大しており、特に、Ｒ２２／ＨＦＰが大きいほど、その効果は顕著であることが分かる。また、例２、例５～例７では、その他の例よりもＨＦＰ分離率が若干劣るが、リボイラー負荷が小さくなっていることがわかる。 In Examples 2 to 10, HFO-1234yf and HFP are separated with high accuracy. As a result, a distillate mainly containing an azeotropic composition or an azeotrope-like composition of HFP and R22 is obtained as a distillate, and HFO-1234yf from which HFP is separated is obtained as a distillate. At this time, the recovery rate of HFP in the distillate improves as R22 / HFP increases. In Examples 2 to 10, it can be seen that the amount of HFO-1234yf relative to HFP in the bottoms is remarkably increased. In particular, the larger R22 / HFP is, the more remarkable the effect is. In Examples 2 and 5 to 7, the HFP separation rate is slightly inferior to the other examples, but it can be seen that the reboiler load is small.
（例１１）
　それぞれ５００℃に予熱したＲ２２およびＲ４０（以下、原料ガスという。）を電気炉内の反応器に連続的に導入し、さらに、８００℃に加熱されたスチーム（水蒸気）を反応器に導入した。反応器内の温度および圧力(ゲージ圧)はそれぞれ実測値で、温度７７０℃、圧力０．０４ＭＰａであった。反応器内の原料ガスの滞留時間が１秒間となるように、原料ガスの流量（単位時間当たりの供給量）を制御し、生成したガスを反応器の出口より取り出した。次いで、反応器の出口より取り出したガスを、１００℃以下に冷却し、蒸気および酸性液の回収とアルカリ洗浄を順に行ってから脱水処理して蒸留用組成物１１とした。この蒸留用組成物１１の組成をガスクロマトグラフィーで分析したところ、表１１に示すようであった。 (Example 11)
R22 and R40 (hereinafter referred to as source gas) each preheated to 500 ° C. were continuously introduced into the reactor in the electric furnace, and steam (water vapor) heated to 800 ° C. was further introduced into the reactor. The temperature and pressure (gauge pressure) in the reactor were measured values, respectively, and the temperature was 770 ° C. and the pressure was 0.04 MPa. The flow rate of the source gas (amount supplied per unit time) was controlled so that the residence time of the source gas in the reactor was 1 second, and the generated gas was taken out from the outlet of the reactor. Next, the gas taken out from the outlet of the reactor was cooled to 100 ° C. or lower, and after steam and acidic liquids were collected and alkali washed sequentially, dehydration treatment was performed to obtain a composition 11 for distillation. When the composition of this distillation composition 11 was analyzed by gas chromatography, it was as shown in Table 11.
　次いで、得られた蒸留用組成物１１を、理論段数５５段の蒸留塔の塔底に供給し、運転圧力０．９ＭＰａ(ゲージ圧)、塔頂温度２９℃となるまでバッチ蒸留による蒸留を行った。例１１におけるＲ２２／ＨＦＰは４３．４である。１．３７ｇ／分で留出液１１を抜き出して回収しながら蒸留を行い、蒸留開始から１，８３０分経過後、留出液１１の抜き出しを停止して塔底部の温度を常温程度に下げ、残った缶出液１１を回収した。蒸留中、塔底温度は３７～４０℃に保たれた。 Next, the obtained composition for distillation 11 is supplied to the bottom of a distillation column having 55 theoretical plates, and distillation by batch distillation is performed until the operating pressure becomes 0.9 MPa (gauge pressure) and the top temperature reaches 29 ° C. It was. R22 / HFP in Example 11 is 43.4. Distillation is conducted while extracting and collecting the distillate 11 at 1.37 g / min. After 1,830 minutes from the start of distillation, the extraction of the distillate 11 is stopped and the temperature at the bottom of the column is lowered to about room temperature. The remaining bottoms 11 was collected. During the distillation, the column bottom temperature was maintained at 37-40 ° C.
　例１１で得られた留出液１１および缶出液１１のそれぞれの組成をガスクロマトグラフィーで分析した。留出液１１および缶出液１１に含有される化合物の質量を表１３に示す。例１１では、ＨＦＯ－１２２５ｙｅおよびＨＦＯ－１１３２については特にＥ体とＺ体を別々に分析した。 Each composition of the distillate 11 and the bottoms 11 obtained in Example 11 was analyzed by gas chromatography. Table 13 shows the mass of the compound contained in the distillate 11 and the bottom 11. In Example 11, with regard to HFO-1225ye and HFO-1132, the E form and the Z form were analyzed separately.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
　表１３より、留出液１１中に蒸留用組成物１１中のＨＦＰの９９％以上が分離され、缶出液１１中に蒸留用組成物１１中の、ＨＦＰと沸点の近い含フッ素化合物（Ａ）およびＲ４０のそれぞれ９５％以上が分離されていることが分かる。 From Table 13, 99% or more of HFP in the composition 11 for distillation was isolate | separated in the distillate 11, and the fluorine-containing compound (A with a boiling point near HFP in the composition 11 for distillation in the bottom 11 is obtained. ) And R40 are each separated by 95% or more.
（例１２）
　ＨＦＰおよびＨＦＯ－１２３４ｙｆを、ＨＦＰの１モルに対してＨＦＯ－１２３４ｙｆを１００モル含み、Ｒ２２を含まない組成物１２を調製する。この組成物１２を、例１と同様の蒸留装置を用いて例１と同様の条件で蒸留を行う。塔頂より留出液１２を、塔底より缶出液１２を例１と同様に回収する。例１２の蒸留条件、例１２で得られる留出液１２と缶出液１２の組成及びリボイラー負荷を表１４に示す。なお、例１２における蒸留用組成物１２のＨＦＯ－１２３４ｙｆ／（ＨＦＯ－１２３４ｙｆ＋ＨＦＰ）×１００は９９．０１０［モル％］である。 (Example 12)
A composition 12 containing 100 moles of HFO-1234yf and 1 mole of HFP and no R22 is prepared with HFP and HFO-1234yf. This composition 12 is distilled under the same conditions as in Example 1 using the same distillation apparatus as in Example 1. The distillate 12 is recovered from the top of the column, and the bottom 12 is recovered from the bottom of the column in the same manner as in Example 1. Table 14 shows the distillation conditions of Example 12, the composition of the distillate 12 and the bottoms 12 obtained in Example 12, and the reboiler load. The HFO-1234yf / (HFO-1234yf + HFP) × 100 of the composition for distillation 12 in Example 12 is 99.010 [mol%].
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
　表１４より、Ｒ２２を含有しない組成物１２では、缶出液１２中のＨＦＰに対するＨＦＯ－１２３４ｙｆの量（モル％）は蒸留前の組成物１２からほとんど変化していないことが分かる。このように、組成物がＲ２２を含まない場合には、含フッ素化合物（Ａ）とＨＦＰとがほとんど分離されないことが分かる。 From Table 14, it can be seen that in the composition 12 not containing R22, the amount (mol%) of HFO-1234yf relative to HFP in the bottoms 12 is almost unchanged from the composition 12 before distillation. Thus, when a composition does not contain R22, it turns out that a fluorine-containing compound (A) and HFP are hardly isolate | separated.
　以上、本発明の実施形態によれば、ＨＦＰと当該ＨＦＰと沸点が近い含フッ素化合物（Ａ）を効率よく分離することができる。 As described above, according to the embodiment of the present invention, HFP and the fluorine-containing compound (A) having a boiling point close to that of HFP can be efficiently separated.
　本発明の分離方法によれば、ＨＦＰと当該ＨＦＰと沸点が近い含フッ素化合物を効率よく分離することができる。
　なお、２０１３年９月２７日に出願された日本特許出願２０１３－２０１４９５号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 According to the separation method of the present invention, HFP and a fluorine-containing compound having a boiling point close to that of HFP can be efficiently separated.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2013-201495 filed on September 27, 2013 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (10)

  1. 　（ａ）ヘキサフルオロプロペン、該ヘキサフルオロプロペンの沸点の－１０℃から＋１５℃の沸点を有する含フッ素化合物およびクロロジフルオロメタンを含む蒸留用組成物を準備する工程と、
    　（ｂ）前記ヘキサフルオロプロペンおよび前記クロロジフルオロメタンの共沸組成物または共沸様組成物を含む留分が形成される蒸留に前記蒸留用組成物を供する工程と
    　を含むことを特徴とするヘキサフルオロプロペンと該ヘキサフルオロプロペンの沸点の－１０℃から＋１５℃の沸点を有する含フッ素化合物の分離方法。     (A) preparing a distillation composition comprising hexafluoropropene, a fluorine-containing compound having a boiling point of −10 ° C. to + 15 ° C. of the boiling point of the hexafluoropropene, and chlorodifluoromethane;
    (B) providing the distillation composition to a distillation in which a fraction containing an azeotropic or azeotrope-like composition of the hexafluoropropene and the chlorodifluoromethane is formed. A method for separating fluoropropene and a fluorine-containing compound having a boiling point of −10 ° C. to + 15 ° C. of the boiling point of hexafluoropropene.
  2. 　前記蒸留用組成物におけるヘキサフルオロプロペンのモル量に対する前記留分中のヘキサフルオロプロペンのモル量の割合は７５％以上であり、かつ前記蒸留用組成物における前記含フッ素化合物のモル量に対する前記留分中の前記含フッ素化合物のモル量の割合は２５％以下である請求項１に記載の分離方法。 The ratio of the molar amount of hexafluoropropene in the fraction relative to the molar amount of hexafluoropropene in the distillation composition is 75% or more, and the distillation relative to the molar amount of the fluorine-containing compound in the distillation composition. The separation method according to claim 1, wherein the proportion of the molar amount of the fluorine-containing compound in the minute is 25% or less.
  3. 　前記蒸留用組成物における前記クロロジフルオロメタンの量は、前記ヘキサフルオロプロペンの１モルに対して３～１００モルである請求項１又は２に記載の分離方法。 The separation method according to claim 1 or 2, wherein the amount of the chlorodifluoromethane in the distillation composition is 3 to 100 moles per mole of the hexafluoropropene.
  4. 　前記蒸留用組成物の全量に対する前記含フッ素化合物の量の割合が１０モル％以上である請求項１～３のいずれか１項に記載の分離方法。 The separation method according to any one of claims 1 to 3, wherein the ratio of the amount of the fluorine-containing compound to the total amount of the distillation composition is 10 mol% or more.
  5. 　前記含フッ素化合物は、クロロペンタフルオロエタン、フルオロエタン、オクタフルオロプロパン、３，３－ジフルオロプロペン、ジクロロジフルオロメタン、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、１，１，１，２－テトラフルオロエタン、１－クロロ－１－フルオロエチレン、１，２－ジフルオロエチレン（Ｚ）、３，３，３－トリフルオロプロペン、１，１－ジフルオロエタン、１－クロロ－１－フルオロエタン、１，１，２，２－テトラフルオロエタン、１，１，３，３，３－ペンタフルオロプロペン、１，１，２，３，３－ペンタフルオロプロペン、１，２，３，３，３－ペンタフルオロプロペン（Ｚ）、１，２，３，３，３－ペンタフルオロプロペン（Ｅ）、１，３，３，３－テトラフルオロプロペン（Ｚ）、１，３，３，３－テトラフルオロプロペン（Ｅ）、１，１，１，２，２－ペンタフルオロプロパン、１－フルオロプロペン（Ｚ）、１－フルオロプロペン（Ｅ）、２－フルオロプロペン、ヘキサフルオロアセトン、１，１，１，２，３，３，３－ヘプタフルオロプロパン、１，１，１，２，２，３，３－ヘプタフルオロプロパン、ヘキサフルオロプロピレンオキサイド、１－クロロ－１，２－ジフルオロエチレンおよび１－クロロ－２，２－ジフルオロエチレンからなる群から選ばれる１種以上を含む請求項１～４のいずれか１項に記載の分離方法。 The fluorine-containing compound is chloropentafluoroethane, fluoroethane, octafluoropropane, 3,3-difluoropropene, dichlorodifluoromethane, 2,3,3,3-tetrafluoropropene, chlorotrifluoroethylene, 1,1, 1,2-tetrafluoroethane, 1-chloro-1-fluoroethylene, 1,2-difluoroethylene (Z), 3,3,3-trifluoropropene, 1,1-difluoroethane, 1-chloro-1-fluoro Ethane, 1,1,2,2-tetrafluoroethane, 1,1,3,3,3-pentafluoropropene, 1,1,2,3,3-pentafluoropropene, 1,2,3,3 3-pentafluoropropene (Z), 1,2,3,3,3-pentafluoropropene (E), 1,3,3,3-tetrafluor Propene (Z), 1,3,3,3-tetrafluoropropene (E), 1,1,1,2,2-pentafluoropropane, 1-fluoropropene (Z), 1-fluoropropene (E), 2-fluoropropene, hexafluoroacetone, 1,1,1,2,3,3,3-heptafluoropropane, 1,1,1,2,2,3,3-heptafluoropropane, hexafluoropropylene oxide, The separation method according to any one of claims 1 to 4, comprising one or more selected from the group consisting of 1-chloro-1,2-difluoroethylene and 1-chloro-2,2-difluoroethylene.
  6. 　前記含フッ素化合物は、２，３，３，３－テトラフルオロプロペン、３，３，３－トリフルオロプロペン、クロロトリフルオロエチレン、３，３－ジフルオロプロペンおよび１，３，３，３－テトラフルオロプロペン（Ｚ）、１，３，３，３－テトラフルオロプロペン（Ｅ）からなる群から選ばれる１種以上を含む請求項１～５のいずれか１項に記載の分離方法。 The fluorine-containing compounds are 2,3,3,3-tetrafluoropropene, 3,3,3-trifluoropropene, chlorotrifluoroethylene, 3,3-difluoropropene and 1,3,3,3-tetrafluoro. The separation method according to any one of claims 1 to 5, comprising one or more selected from the group consisting of propene (Z) and 1,3,3,3-tetrafluoropropene (E).
  7. 　前記含フッ素化合物は、２，３，３，３－テトラフルオロプロペンを含む請求項１～６のいずれか１項に記載の分離方法。 The separation method according to any one of claims 1 to 6, wherein the fluorine-containing compound contains 2,3,3,3-tetrafluoropropene.
  8. 　前記蒸留が、ゲージ圧で０．２～２．０ＭＰaで行われる請求項１～７のいずれか１項に記載の分離方法。 The separation method according to any one of claims 1 to 7, wherein the distillation is performed at a gauge pressure of 0.2 to 2.0 MPa.
  9. 　前記蒸留用組成物がクロロメタンを含む請求項１～８のいずれか１項に記載の分離方法。 The separation method according to any one of claims 1 to 8, wherein the distillation composition contains chloromethane.
  10. 　前記共沸様組成物の組成範囲が、比揮発度が１．００±０．２０となる範囲である請求項１～９のいずれか１項に記載の分離方法。 The separation method according to any one of claims 1 to 9, wherein the composition range of the azeotrope-like composition is a range in which the relative volatility is 1.00 ± 0.20.
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