(19)
(11)EP 2 939 994 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
18.07.2018 Bulletin 2018/29

(21)Application number: 13866573.2

(22)Date of filing:  21.11.2013
(51)Int. Cl.: 
C07C 17/386  (2006.01)
C07C 19/03  (2006.01)
C07C 21/18  (2006.01)
(86)International application number:
PCT/JP2013/081448
(87)International publication number:
WO 2014/103582 (03.07.2014 Gazette  2014/27)

(54)

METHOD FOR PURIFYING TETRAFLUOROPROPENE

VERFAHREN ZUR REINIGUNG VON TETRAFLUORPROPEN

PROCÉDÉ POUR LA PURIFICATION DE TÉTRAFLUOROPROPÈNE


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 27.12.2012 JP 2012285248

(43)Date of publication of application:
04.11.2015 Bulletin 2015/45

(73)Proprietor: Asahi Glass Company, Limited
Tokyo 100-8405 (JP)

(72)Inventors:
  • FURUTA, Shoji
    Tokyo 100-8405 (JP)
  • OTSUKA, Tetsuo
    Tokyo 100-8405 (JP)

(74)Representative: Müller-Boré & Partner Patentanwälte PartG mbB 
Friedenheimer Brücke 21
80639 München
80639 München (DE)


(56)References cited: : 
WO-A1-2011/030026
WO-A1-2012/105700
WO-A1-2015/053339
JP-A- 2009 513 719
WO-A1-2012/011609
WO-A1-2013/154059
JP-A- 2008 506 793
JP-A- 2010 202 640
  
     
    Remarks:
    The file contains technical information submitted after the application was filed and not included in this specification
     
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description


    [0001] The present invention relates to a method to obtain 2,3,3,3-tetrafluoropropene (hereinafter sometimes referred to as "HFO-1234yf") or chloromethane (hereinafter sometimes referred to as "R40") from a composition containing 2,3,3,3-tetrafluoropropene and chloromethane.

    [0002] 2,3,3,3-tetrafluoropropene has attracted attention as a new refrigerant to be substituted for 1,1,1,2-tetrafluoroethane (HFC-134a) which is a greenhouse gas.

    [0003] Here, in this specification, with respect to a halogenated hydrocarbon, in brackets after its chemical name, an abbreviated name of the compound is indicated, and as the case requires, instead of the chemical name, its abbreviated name is used.

    [0004] Further, a method for producing HFO-1234yf by one reaction involving thermal decomposition, from a raw material containing a chlorofluorocarbon, has been proposed.

    [0005] As such a method, for example, Patent Document 1 proposes a method to obtain HFO-1234yf by heating and decomposing a mixture of chloromethane (R40) and chlorodifluorormethane (R22) and/or tetrafluoroethylene (TFE) to a temperature of from 700 to 950°C in a reactor by means of a conventional heating means such as an electric heater (Patent Document 1).

    [0006] Here, in a case where HFO-1234yf is to be produced by the above method, the obtainable reaction mixture contains, in addition to the desired substance HFO-1234yf, unreacted raw materials such as R40. From an industrial viewpoint, in addition to purifying the reaction mixture to obtain HFO-1234yf as a product, recycle of R40 for the reaction by purification from the reaction mixture has also been desired.

    [0007] Patent document 2 provides a method for purifying R-1234yf, whereby it is possible to efficiently remove even impurities such as R-1243zf which are difficult to separate by distillation purification, from a mixture containing R-1234yf as the main component and various impurities, such as a gas formed by reacting R-1214ya with hydrogen.

    Patent Document 1: U.S. Patent No. 2,931,840

    Patent Document 2: WO 2012/105700 A1



    [0008] The boiling points of HFO-1234yf and R40 are respectively -29°C and -24°C (under atmospheric pressure) and close to each other and thus separation of them by distillation is difficult.

    [0009] In the method disclosed in the above background art, as a method for producing HFO-1234yf, the raw material R40 is included, and thus a method to efficiently obtain HFO-1234yf or R40 from a composition containing HFO-1234yf and R40 has been desired.

    [0010] The present inventors have found that when HFO-1234yf and R40 are to be separated from a composition containing them, an azeotropic composition or azeotrope-like composition forms, and they cannot readily be separated.

    [0011] To separate a composition which is difficult to separate by conventional distillation, a separation method characterized by bringing the composition into contact with a compound having compatibility with a certain substance in the composition, for example, extractive distillation or absorption, has been known.

    [0012] When such separation by extractive distillation or absorption is applied to a composition containing HFO-1234yf and R40, it is necessary to use a compound having a high relative volatility of HFO-1234yf based on R40. However, it is difficult to predict the relative volatility of HFO-1234yf based on R40 with respect to a certain compound, or to predict the relative volatility of R40 based on HFO-1234yf with respect to a certain substance. Thus, in the method of separating, for example, HFO-1234yf from R40, by extractive distillation, absorption or the like, it is not possible to predict which substance should be used.

    [0013] Under these circumstances, it is an object of the present invention to provide a method for efficiently separating HFO-1234yf or R40 from a composition containing HFO-1234yf and R40.

    [0014] The present inventors have found it possible to separate HFO-1234yf and R40 from an azeotropic composition or azeotrope-like composition of them and further found a solvent to efficiently separate them, and accomplished the present invention.

    [0015] That is, the present inventors have conducted extensive studies on various substances and as a result, found that the relative volatility of HFO-1234yf based on R40 changes by bringing the azeotropic composition or azeotrope-like composition into contact with a specific compound, and accomplished the present invention.

    [0016] That is, the present invention provides the following.
    1. 1. A method for producing 2,3,3,3-tetrafluoropropene, which comprises binging an azeotropic composition or azeotrope-like composition of 2,3,3,3-tetrafluoropropene and chloromethane into contact with pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, methanol, ethanol, propanol, butanol, pentanol, CF3CH2OCF2CF2H, CF3CF2CF2CF2OCF3, CF3CF2CF2CF2OCH2CH3, CClF2CF2CHClF, CF3CF2CF2CF2CF2CF2CH2CH3 or CF3CF2CHFCHFCF3 to obtain 2,3,3,3-tetrafluoropropene containing substantially no chloromethane, wherein the azeotrope-like composition is a composition wherein the content ratio of 2,3,3,3-tetrafluoropropene is from 58 to 78 mol%, and the content ratio of chloromethane is from 22 to 42 mol%.
    2. 2. A method for producing chloromethane containing substantially no 2,3,3,3-tetrafluoropropene from an azeotropic composition or azeotrope-like composition of 2,3,3,3-tetrafluoropropene and chloromethane, which comprises bringing the composition into contact with CF3CF2CF2CF2CF2CF2H or CF3CF2CF2CF2CF2CF3, wherein the azeotrope-like composition is a composition wherein the content ratio of 2,3,3,3-tetrafluoropropene is from 58 to 78 mol%, and the content ratio of chloromethane is from 22 to 42 mol%.


    [0017] According to the present invention, a method for efficiently separating 2,3,3,3-tetrafluoropropene (HFO-1234yf) and chloromethane (R40) from a composition containing HFO-1234yf and R40.

    [0018] Fig. 1 is a view schematically illustrating a method for efficiently separating 2,3,3,3-tetrafluoropropene (HFO-1234yf) and chloromethane (R40) from a composition containing HFO-1234yf and R40.

    [Azeotropic composition]



    [0019] An azeotropic composition comprising HFO-1234yf and R40 of the present invention is a composition wherein the content ratio of HFO-1234yf is 63 mol%, and the content ratio of R40 is 37 mol%, and has a boiling point of 41.3°C under a pressure of 1.011x106Pa. The azeotropic composition undergoes no change in its composition when repeatedly subjected to distillation and condensation and thus has such a merit that when it is used in an application to a refrigerant or the like, an extremely stable performance is obtainable. Further, the azeotropic composition has a relative volatility of 1.00 as represented by the following formula.


    [Azeotrope-like composition]



    [0020] The azeotrope-like composition comprising HFO-1234yf and R40 of the present invention is a composition wherein the content ratio of HFO-1234yf is from 58 to 78 mol%, and the content ratio of R40 is from 22 to 42 mol%. It undergoes little change in its composition when repeatedly subjected to distillation and condensation. Here, in this specification, an azeotrope-like composition is a composition wherein the relative volatility obtained by the above formula is within a range of 1.00±0.20. Further, the azeotrope-like composition comprising HFO-1234yf and R40 of the present invention has a boiling point of from 41 to 42°C under a pressure of 1.011x106Pa.

    [0021] The azeotrope-like composition of the present invention can be handled substantially in the same manner as the above-described azeotropic composition of the present invention and has such a merit that when it is used in an application to a refrigerant or the like, a stable performance equal to the azeotropic composition is obtainable. Further, in the following description, the azeotrope-like composition will be described as including the azeotropic composition.

    [0022] In this specification, the term "extractive distillation" is used in a sense used in the technical field of the present invention particularly in the chemical engineering field, and is one type of distillation separation method to be used to separate an azeotropic composition or a liquid composition which is difficult to separate by distillation separation since the boiling points are close to each other.

    [0023] In the extractive distillation, by adding a third component to a composition mainly comprising two components, the relative volatility of the original composition mainly comprising two components is changed so as to ease the distillation separation. The third component here is called an extraction solvent in this specification.

    [0024] The extraction solvent is a compound which may be used for extractive distillation and may be one which is not liquid at room temperature, but is present as a liquid when the extractive distillation is carried out. By adding this extraction solvent to an azeotropic composition or a liquid composition which is difficult to separate by distillation separation since the boiling points are close to each other, it is possible to separate either one of the two components, which is not absorbed in the extraction solvent, that is, either component to be separated. Further, the azeotropic composition may contain a small amount of other components.

    [0025] The present invention provides a method for separating HFO-1234yf containing substantially no R40 from a composition containing HFO-1234yf and R40, which comprises bringing the composition into contact with pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, methanol, ethanol, propanol, butanol, pentanol, CF3CH2OCF2CF2H, CF3CF2CF2CF2OCF3, CF3CF2CF2CF2OCH2CH3, CClF2CF2CHClF, CF3CF2CF2CF2CF2CF2CH2CH3 or CF3CF2CHFCHFCF3, wherein the azeotrope-like composition is a composition wherein the content ratio of 2,3,3,3-tetrafluoropropene is from 58 to 78 mol%, and the content ratio of chloromethane is from 22 to 42 mol%.

    [0026] The present invention further provides a method for separating R40 containing substantially no HFO-1234yf from a composition containing HFO-1234yf and R40, which comprises bringing the composition into contact with CF3CF2CF2CF2CF2CF2H or CF3CF2CF2CF2CF2CF3, wherein the azeotrope-like composition is a composition wherein the content ratio of 2,3,3,3-tetrafluoropropene is from 58 to 78 mol%, and the content ratio of chloromethane is from 22 to 42 mol%.

    [0027] It is difficult to separate HFO-1234yf and R40 from a composition containing them by distillation since their boiling points are close to each other. In a case where separation by extractive distillation is applied to a composition containing HFO-1234yf and R40, to separate HFO-1234yf for example, it is necessary to use a solvent with a high relative volatility of HFO-1234yf based on R40.

    [0028] Thus, the present inventors have conductive studies and as a result, found that HFO-1234yf containing substantially no R40 can be separated from a composition containing HFO-1234yf and R40 by using a specific extraction solvent.

    [0029] Further, they have hound that R40 containing substantially no HFO-1234yf can be separated from a composition containing HFO-1234yf and R40 by using a specific extraction solvent.

    [0030] The present inventors have conducted studies on effects by the respective compounds in a method for separating HFO-1234yf by extractive distillation from a composition containing HFO-1234yf and R40. As a result, they have obtained results as mentioned hereinafter with respect to the above-described relative volatility.

    [0031] Heretofore, it has been known that the gas-liquid equilibrium of two components changes in some cases by the presence of a specific compound. In a case where such a compound affects the gas-liquid equilibrium, the relative volatility obtained by the above formula changes.

    [0032] A compound which may change the relative volatility is called an extraction solvent in this specification.

    [0033] The relative volatility in a state where no extraction solvent is added (two-components) and the relative volatility when an extraction solvent is added, are compared. It is understood that if the value obtainable by the above formula is increased, such an extraction solvent is an extraction solvent which absorbs R40. By using such an extraction solvent, it is possible to separate 1234yf from a composition containing HFO-1234yf and R40 by extractive distillation.

    [0034] Whereas, when the value obtainable by the above formula is decreased, such an extraction solvent is considered to be an extraction solvent which absorbs HFO-1234yf. By using such an extraction solvent, it is possible to separate R40 from a composition containing HFO-1234yf and R40 by extractive distillation.

    [0035] In this specification, an extraction solvent means a solvent which is liquid at room temperature under normal pressure, however, a solvent which is present as a liquid under reaction conditions in a distillation tower for example, is regarded as the extraction solvent of the present invention.

    <Separation of HFO-1234yf>



    [0036] The extraction solvent in the present invention is as defined in claim 1. It may be pentane, hexane, heptane, octane, nonane, decane, undecane or dodecane. It may preferably be pentane, hexane, heptane, octane, nonane or decane.

    [0037] The extraction solvent according to the present invention may further be methanol, ethanol, propanol, butanol or pentanol. It may preferably be methanol, ethanol or butanol.

    [0038] The extraction solvent in the present invention may further be CF3CH2OCF2CF2H (manufactured by Asahi Glass Company, Limited, tradename: AE3000), tetrafluoropropanol (manufactured by Asahi Glass Company, Limited), CF3CF2CF2CF2OCF3 (manufactured by Sumitomo 3M Limited, tradename: Novec™7100) or CF3CF2CF2CF2OCH2CH3 (manufactured by Sumitomo 3M Limited, tradename: Novec™7200). The extraction solvent in the present invention may further be CClF2CF2CHClF (manufactured by Asahi Glass Company, Limited, tradename; AK225cb), CF3CF2CF2CF2CF2CF2CH2CH3 (manufactured by Asahi Glass Company, Limited, tradename: AC6000) or CF3CF2CHFCHFCF3 (manufactured by Du Pont, tradename: HFC4310).

    <Separation of R40>



    [0039] Further, according to studies by the present inventors, it was found that chloromethane containing substantially no 2,3,3,3-tetrafluoropropene can be separated from a composition containing 2,3,3,3-tetrafluoropropene and chloromethane by using a specific extraction solvent.

    [0040] The extraction solvent in the present invention is CF3CF2CF2CF2CF2CF2H (manufactured by Asahi Glass Company, Limited, tradename: AC2000) or CF3CF2CF2CF2CF2CF3 (manufactured by Sumitomo 3M Limited, tradename: PF-5060).

    [0041] Now, the present invention will be described in further detail with reference to Examples. However, it should be understood that the present invention is by no means restricted thereto.

    <Example in which compound having no fluorine atom is used>


    [Ex. 1]



    [0042] A composition obtained by mixing 176 g of HFO-1234yf, 26 g of R40 and 99 g of methanol was put in a 500 mL autoclave equipped with a pressure meter and gradually heated by an external heater so that the pressure would be 1.011×106Pa. The composition was adjusted so that the ratio by mol% would be solvent: HFO-1234yf:R40=60:30:10. After the pressure in the autoclave reached the prescribed 1.011×106Pa, it was maintained for a certain time to stabilize the composition in the autoclave. A sample of the composition was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the following formula to obtain a relative volatility.


    [Ex. 3, Ex. 5 and Ex. 6]



    [0043] In the same manner as in Ex. 1 except that the solvent was changed to a solvent as identified in Table 1, a sample was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility.
    [Table 1]
     Solvent usedSolvent charged amount [g]HFO-1234yf charged amount [g]R40 charged amount [g]
    Ex.1 Methanol 99 176 26
    Ex.3 Decane 91 37 5
    Ex.5 Ethanol 99 122 18
    Ex.6 Hexane 82 54 8
    Ex.16 Nil 0 186 28


    [0044] The results are shown in Table 2. The relative volatility when a non-fluorinated solvent was used was higher than the relative volatility of 0.904 when no solvent was used. This is considered to result from a change in the gas-liquid equilibrium between HFO-1234yf and R40 due to the presence of the non-fluorinated solvent, thus leading to an increase in HFO-1234yf in the gas phase.
    [Table 2]
     Solvent usedRelative volatility
    Ex.1 Methanol 1.201
    Ex.3 Decane 1.424
    Ex.5 Ethanol 1.911
    Ex.6 Hexane 2.036
    Ex.16 Nil 0.904

    <Example of fluorinated compound having fluorination degree of less than 0.8 and having polar group>


    [Ex. 16]



    [0045] A composition obtained by mixing 186 g of HFO-1234yf and 28 g of R40 was put in a 500 mL autoclave equipped with a pressure meter and gradually heated by an external heater so that the pressure would be 1.011×106Pa. After the pressure in the autoclave reached the prescribed 1.011×106 Pa, it was maintained for a certain time to stabilize the composition in the autoclave. A sample of the composition was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility. The results are shown in Table 4.

    [Ex. 17 to 20]



    [0046] In the same manner as in Ex. 1 except that the solvent was changed to a solvent as identified in Table 3, a sample was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility. The results are shown in Table 4.
    [Table 3]
     Solvent usedFluorination degreeSolvent charged amount [g]HFO-1234yf charged amount [g]R40 charged amount [g]
    Ex.17 AE3000 0.700 184 53 8
    Ex.18 2,3,3,3-tetrafluoropropanol 0.500 185 81 12
    Ex.19 Novec™7100 0.750 190 43 6
    Ex.20 Novec™ 7200 0.643 179 39 6
    Ex.16 Nil -- 0 186 28
    [Table 4]
     Solvent usedFluorination degreeRelative volatility
    Ex.17 AE3000 0.700 1.405
    Ex.18 2,3,3,3-tetrafluoropropanol 0.500 1.837
    Ex.19 Novec™7100 0.750 1.119
    Ex.20 Novec™7200 0.643 1.082
    Ex.16 Nil -- 0.904


    [0047] As shown in Table 4, when a fluorinated solvent having a fluorination degree of less than 0.8 was used, the relative volatility was higher than in Ex. 16 in which no solvent was used. This is considered to result from transfer of R40 in the gas phase to the liquid phase by the effect of the fluorinated solvent having a fluorination degree of less than 0.8, thus leading to concentration of HFO-1234yf in the gas phase.

    <Example of fluorinated compound having fluorination degree of less than 0.9 and having no polar group>


    [Ex. 21]



    [0048] A composition obtained by mixing 55 g of HFO-1234yf, 8 g of R40 and 195 g of CClF2CF2CHClF (AK225cb) was put in a 500 mL autoclave equipped with a pressure meter and gradually heated by an external heater so that the pressure would be 1.011×106Pa. After the pressure in the autoclave reached the prescribed 1.011×106Pa, it was maintained for a certain time to stabilize the composition in the autoclave. A sample of the composition was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility. The results are shown in Table 6.

    [Ex. 22 and 23]



    [0049] In the same manner as in Ex. 21 except that the solvent used, and the amounts of charge of HFO-1234yf, R40 and the solvent were changed as identified in Table 5, a sample was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility. The results are shown in Table 6.[Table 5]
     Solvent usedFluorination degreeSolvent charged amount [g]HFO-1234yf charged amount [g]R40 charged amount [g]
    Ex.21 AK225cb 0.833 195 55 8
    Ex.22 AC6000 0.722 195 32 5
    Ex.23 HFC4310 0.833 198 45 7
    Ex.16 Nil -- 0 186 28
    [Table 6]
     Solvent usedFluorination degreeRelative volatility
    Ex.21 AK225cb 0.833 1.441
    Ex.22 AC6000 0.722 1.120
    Ex.23 HFC4310 0.833 1.092
    Ex.16 Nil -- 0.904


    [0050] As shown in Table 6, when a fluorinated solvent having a fluorination degree of less than 0.9 was used, the relative volatility was higher than in Ex. 16 in which no solvent was used. This is considered to result from transfer of R40 in the gas phase to the liquid phase by the effect of the fluorinated solvent having a fluorination degree of less than 0.9, thus leading to concentration of HFO-1234yf in the gas phase.

    <Example of fluorinated compound having fluorination degree of at least 0.9 and having no polar group>


    [Ex. 28]



    [0051] A composition obtained by mixing 37 g of HFO-1234yf, 5 g of R40 and 209 g of tridecafluorohexane (AC2000) was put in a 500 mL autoclave equipped with a pressure meter and gradually heated by an external heater so that the pressure would be 1.011×106Pa. After the pressure in the autoclave reached the prescribed 1.011×106Pa, it was maintained for a certain time to stabilize the composition in the autoclave. A sample of the composition was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility. The results are shown in Table 10.

    [Ex. 29]



    [0052] In the same manner as in Ex. 28 except that the solvent was changed to perfluorohexane, a sample was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility.

    [Ex. 30]



    [0053] A composition obtained by mixing 143 g of HFO-1234yf and 63 g of R40 was put in a 500 mL autoclave equipped with a pressure meter and gradually heated by an external heater so that the pressure would be 1.011×106Pa. After the pressure in the autoclave reached the prescribed 1.011×106Pa, it was maintained for a certain time to stabilize the composition in the autoclave. A sample of the composition was taken from the gas phase and the liquid phase, and HFO-1234yf and R40 were analyzed by gas chromatography to measure the compositional ratios of the two. From the compositional ratios of the two, the relative volatility was obtained by the formula to obtain a relative volatility. The results are shown in Tables 9, 10 and 12.
    [Table 10]
     Solvent usedFluorination degreeSolvent charged amount [g]HFO-1234yf charged amount [g]R40 charged amount [g]
    Ex.28 AC2000 0.929 209 25 11
    Ex.29 PF-5060 1 210 59 9
    Ex.16 Nil -- 0 186 28
    Ex.30 Nil -- 0 143 63
    [Table 11]
     Solvent usedFluorination degreeRelative volatility
    Ex.29 PF-5060 1 0.788
    Ex.16 Nil -- 0.904
    [Table 12]
     Solvent usedFluorination degreeRelative volatility
    Ex.28 AC2000 0.929 0.987
    Ex.30 Nil -- 1.186


    [0054] As shown in Table 11, when a fluorinated solvent having a fluorination degree of at least 0.9 was used, the relative volatility was lower than in Ex. 16 in which no solvent was used. Further, as shown in Table 12, when a fluorinated solvent having a fluorination degree of at least 0.9 was used, the relative volatility was lower than in Ex. 30 in which no solvent was used. This is considered to result from concentration of HFO-1234yf in the liquid phase by the effect of the fluorinated solvent having a fluorination degree of at least 0.9.

    <Extractive distillation>



    [0055] A composition 1 containing HFO-1234yf and R40 is supplied to an extractive distillation tower 2 operated under elevated pressure. Of the extractive distillation tower 2, the number of theoretical plates and the operation conditions are properly set depending upon the solvent to be used, the purity of HFO-1234yf desired as a distillate 4, etc. The composition 1 supplied to the extractive distillation tower 2 is distilled while being contacted with an extracting agent 3 as an extraction solvent. In a case where an extraction solvent having high compatibility with R40 is used as an extracting agent 3, a distillate 4 having an increased concentration of HFO-1234yf than the composition 1 can be obtained from the top of the distillation tower, and a bottom product 5 having an increased concentration of R40 than the composition 1 can be obtained.

    [0056] Further, in a case where an extraction solvent having high compatibility with HFO-1234yf is used as an extracting agent 3, a distillate 4 having a higher purity of R40 than the composition 1 can be obtained from the top of the distillation tower, and a bottom product 5 having an increased concentration of HFO-1234yf than the composition 1 can be obtained. By supplying the bottom product to a solvent recovery tower 6 operated under elevated pressure, when an extraction solvent having high compatibility with R40 is used as an extracting agent 3 in the extractive distillation tower 2 for example, a distillate 7 having an increased concentration of R40 than the composition 1 can be obtained from the top of the distillation tower. Further, by supplying the bottom product 5 to the solvent recovery tower 6 operated under elevated pressure, when an extraction solvent having high compatibility with HFO-1234yf is used as an extracting agent 3 in the extractive distillation tower 2 for example, a distillate 7 having a higher purity of HFO-1234yf than the composition 1 can be obtained from the top of the distillation tower.

    [0057] Further, from the tower bottom of the solvent recovery tower 6, an extraction solvent containing substantially no HFO-1234yf and R40 is recovered as a bottom product 8, and the obtained bottom product is heated or cooled by a heat exchanger 9 as the case requires and is supplied to the extractive distillation tower 2 and recycled as the extracting agent 3 as the extraction solvent.

    <Example 3>



    [0058] The present invention is carried out using 1,3-dichloro-1,1,2,2,3-pentafluoropropane (AK225cb) as an extraction solvent by simulation.

    [0059] To an extractive distillation tower with 5 theoretical plates at a solvent recovery portion, 40 theoretical plates at a concentration portion and 5 theoretical plates at a recovery portion, a composition of HFO-1234yf and R40 (in a molar ratio of 6:4) is continuously supplied at a rate of 89 g per hour from the lower portion of the concentration portion, and 1,3-dichloro-1,1,2,2,3-pentafluoropropane as an extraction solvent is continuously supplied at a rate of 2,029 g per hour from the lower portion of the solvent recovery portion. Further, while the reflux ratio is controlled to be 1.5 on the tower top side, a first fraction is continuously withdrawn at a rate of 63 g per hour, and a second fraction is continuously withdrawn at a rate of 2,055 g per hour on the tower bottom side to conduct extractive distillation. During the extraction distillation, the pressure in the extractive distillation tower (in the system) is 0.5 MPaG (gauge pressure), the tower top temperature is 15°C, and tower bottom temperature is 96°C.

    [0060] In the first fraction obtainable from the extractive distillation tower, R40 is not contained, and the content of HFO-1234yf is 99.8 mol%. Further, the first fraction contains 0.2 mol% of the extraction solvent.

    [0061] Whereas, the content of HFO-1234yf in the second fraction obtainable from the extractive distillation tower is 0.5 mol%, and the content of R40 is 3.9 mol%, and the rest is substantially AK-225cb.

    [0062] The obtainable second fraction is continuously supplied at a rate of 2,055 g per hour to a solvent recovery tower having 40 theoretical plates, from the first plate from the bottom. Further, while the reflux ratio is controlled to be 111 on the tower top side, a third fraction is continuously withdrawn at a rate of 27 g per hour and a fourth fraction is continuously withdrawn at a rate of 2,028 g per hour on the tower bottom side, to conduct recovery distillation. During recovery distillation, the pressure in the solvent recovery tower (in the system) is 0.2 MPaG (gauge pressure), the tower top temperature is 23°C and the tower bottom temperature is 78°C.

    [0063] The content of R40 in the third fraction obtainable from the solvent recovery tower is at least 87 mol%.

    [0064] Whereas, the content of AK-225-cb in the fourth fraction obtainable from the solvent recovery tower is at least 99 mol%. The obtainable fourth fraction is recycled to the extraction distillation tower.

    [0065] According to the method for separating and purifying 2,3,3,3-tetrafluoropropene and chloromethane from a composition containing them by using an extraction solvent of the present invention, a high purity product can be obtained efficiently, and the method is industrially useful.

    REFERENCE SYMBOLS



    [0066] 1: composition, 2: extractive distillation tower, 3: extracting agent, 4: distillate, 5: bottom product, 6: solvent recovery tower, 7: distillate, 8: bottom product, 9: heat exchanger.


    Claims

    1. A method for producing 2,3,3,3-tetrafluoropropene, which comprises bringing an azeotropic composition or azeotrope-like composition of 2,3,3,3-tetrafluoropropene and chloromethane into contact with pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, methanol, ethanol, propanol, butanol, pentanol, CF3CH2OCF2CF2H, CF3CF2CF2CF2OCF3, CF3CF2CF2CF2OCH2CH3, CClF2CF2CHClF, CF3CF2CF2CF2CF2CF2CH2CH3 or CF3CF2CHFCHFCF3 to obtain 2,3,3,3-tetrafluoropropene containing substantially no chloromethane, wherein the azeotrope-like composition is a composition wherein the content ratio of 2,3,3,3-tetrafluoropropene is from 58 to 78 mol%, and the content ratio of chloromethane is from 22 to 42 mol%.
     
    2. A method for producing chloromethane containing substantially no 2,3,3,3-tetrafluoropropene from an azeotropic composition or azeotrope-like composition of 2,3,3,3-tetrafluoropropene and chloromethane, which comprises bringing the composition into contact with CF3CF2CF2CF2CF2CF2H or CF3CF2CF2CF2CF2CF3, wherein the azeotrope-like composition is a composition wherein the content ratio of 2,3,3,3-tetrafluoropropene is from 58 to 78 mol%, and the content ratio of chloromethane is from 22 to 42 mol%.
     


    Ansprüche

    1. Verfahren zum Herstellen von 2,3,3,3-Tetrafluorpropen, welches das Inkontaktbringen einer azeotropen Zusammensetzung oder azeotrop-ähnlichen Zusammensetzung von 2,3,3,3-Tetrafluorpropen und Chlormethan mit Pentan, Hexan, Heptan, Octan, Nonan, Decan, Undecan, Dodecan, Methanol, Ethanol, Propanol, Butanol, Pentanol, CF3CH2OCF2CF2H, CF3CF2CF2CF2OCF3, CF3CF2CF2CF2OCH2CH3, CClF2CF2CHClF, CF3CF2CF2CF2CF2CF2CH2CH3 oder CF3CF2CHFCHFCF3 unter Erhalten von 2,3,3,3-Tetrafluorpropen, enthaltend im wesentlichen kein Chlormethan, umfasst, wobei die azeotrop-ähnliche Zusammensetzung eine Zusammensetzung ist, wobei das Anteilverhältnis von 2,3,3,3-Tetrafluorpropen von 58 bis 78 Mol-% beträgt und das Anteilverhältnis von Chlormethan von 22 bis 42 Mol-% beträgt.
     
    2. Verfahren zur Herstellung von Chlormethan, enthaltend im Wesentlichen kein 2,3,3,3-Tetrafluorpropen, aus einer azeotropen Zusammensetzung oder azeotrop-ähnlichen Zusammensetzung von 2,3,3,3-Tetrafluorpropen und Chlormethan, welches das Inkontaktbringen der Zusammensetzung mit CF3CF2CF2CF2CF2CF2H oder CF3CF2CF2CF2CF2CF3 umfaßt, wobei die azeotrop-ähnliche Zusammensetzung eine Zusammensetzung ist, worin das Anteilverhältnis von 2,3,3,3-Tetrafluorpropen von 58 bis 78 Mol-% beträgt und das Anteilverhältnis von Chlormethan von 22 bis 42 Mol-% beträgt.
     


    Revendications

    1. Procédé pour produire du 2,3,3,3-tétrafluoropropène, qui comprend la mise en contact d'une composition azéotrope ou d'une composition de type azéotrope de 2,3,3,3-tétrafluoropropène et de chlorométhane avec du pentane, de l'hexane, de l'heptane, de l'octane, du nonane, du décane, de l'undécane, du dodécane, du méthanol, de l'éthanol, du propanol, du butanol, du pentanol, CF3CH2OCF2CF2H, CF3CF2CF2CF2OCF3, CF3CF2CF2CF2OCH2CH3, CClF2CF2CHClF, CF3CF2CF2CF2CF2CF2CH2CH3 ou CF3CF2CHFCHFCF3, pour que soit obtenu du 2,3,3,3-tétrafluoropropène ne contenant pratiquement pas de chlorométhane, dans lequel la composition de type azéotrope est une composition dans laquelle la proportion en contenu du 2,3,3,3-tétrafluoropropène est de 58 à 78 % en moles et la proportion en contenu du dichlorométhane est de 22 à 42 % en moles.
     
    2. Procédé pour produire du chlorométhane ne contenant pratiquement pas de 2,3,3,3-tétrafluoropropène à partir d'une composition azéotrope ou d'une composition de type azéotrope de 2,3,3,3-tétrafluoropropène et de chlorométhane, qui comprend la mise en contact de la composition avec CF3CF2CF2CF2CF2CF2H ou CF3CF2CF2CF2CF2CF3, dans lequel la composition de type azéotrope est une composition dans laquelle la proportion en contenu du 2,3,3,3-tétrafluoropropène est de 58 à 78 % en moles et la proportion en contenu du dichlorométhane est de 22 à 42 % en moles.
     




    Drawing






    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description