WO2015053339A1 - Procédé de purification de 2,3,3,3-tétrafluoropropène - Google Patents

Procédé de purification de 2,3,3,3-tétrafluoropropène Download PDF

Info

Publication number
WO2015053339A1
WO2015053339A1 PCT/JP2014/076995 JP2014076995W WO2015053339A1 WO 2015053339 A1 WO2015053339 A1 WO 2015053339A1 JP 2014076995 W JP2014076995 W JP 2014076995W WO 2015053339 A1 WO2015053339 A1 WO 2015053339A1
Authority
WO
WIPO (PCT)
Prior art keywords
hfo
composition
distillation
tetrafluoropropene
fluorine
Prior art date
Application number
PCT/JP2014/076995
Other languages
English (en)
Japanese (ja)
Inventor
優 竹内
哲央 大塚
古田　昇二
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to JP2015541622A priority Critical patent/JP6358263B2/ja
Priority to CN201480055614.8A priority patent/CN105612139B/zh
Publication of WO2015053339A1 publication Critical patent/WO2015053339A1/fr

Links

Classifications

    • 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 purifying 2,3,3,3-tetrafluoropropene, and in particular, has a boiling point close to 2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene.
  • the present invention relates to a method for efficiently purifying 2,3,3,3-tetrafluoropropene from a mixture containing a fluorine-containing compound.
  • HFO-1234yf 2,3,3,3-tetrafluoropropene
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • Patent Document 1 proposes a method of obtaining HFO-1234yf by thermally decomposing a mixture of chloromethane (R40) and chlorodifluoromethane (R22) in the presence of a heat medium. ing.
  • Patent Document 3 describes that HFO-1234yf and hydrogen fluoride form an azeotropic composition and an azeotrope-like composition, and using this, HFO-1234yf and HFO-1234yf are obtained by azeotropic distillation.
  • a technique for separating 1,1,1,2,2-pentafluoropropane (HFC-245cb) is described.
  • HFC-245cb is known as a starting material for the production of HFO-1234yf by vapor phase dehydrofluorination, and separation of HFO-1234yf and unreacted HFC-245cb contained in the resulting reaction product is known. For this reason, the above separation technique is applied.
  • the present invention has been made from the above viewpoint, from a mixture containing 2,3,3,3-tetrafluoropropene and a fluorine-containing compound having a boiling point close to that of 2,3,3,3-tetrafluoropropene. It is an object to provide a method for efficiently purifying 2,3,3,3-tetrafluoropropene.
  • the present invention provides a method for purifying 2,3,3,3-tetrafluoropropene (HFO-1234yf) comprising the following steps (a) to (c).
  • the boiling point of the compound indicates the boiling point at normal pressure (1.013 ⁇ 10 5 Pa).
  • HFO-1234yf can be efficiently purified from a mixture containing HFO-1234yf and a fluorine-containing compound having a boiling point close to that of HFO-1234yf.
  • the purification method of HFO-1234yf of the present invention is a compound having a boiling point close to that of HFO-1234yf and HFO-1234yf (boiling point: ⁇ 29 ° C.), specifically, a fluorine-containing compound having a boiling point of ⁇ 14 ° C. to ⁇ 30 ° C.
  • a fluorine-containing compound (A)) the method aims to purify HFO-1234yf, wherein both HFO-1234yf and R40
  • a step of preparing a distillation composition containing the fluorine-containing compound (A), HFO-1234yf, and R40 (hereinafter, also referred to as “distillation preparation step”).
  • B A step of subjecting the distillation composition to distillation in which a fraction containing an azeotropic composition or an azeotrope-like composition of HFO-1234yf and R40 is formed (hereinafter also referred to as “azeotropic distillation step”).
  • C A step of obtaining purified HFO-1234yf having a higher HFO-1234yf concentration than the above fraction (hereinafter, also referred to as “concentration step”).
  • HFO-1234yf and fluorine-containing compound (A) can be efficiently separated from “crude HFO-1234yf”. That is, according to the purification method of the present invention, the ratio of HFO-1234yf to the fluorine-containing compound (A) in the purified HFO-1234yf obtained (hereinafter sometimes referred to as “HFO-1234yf / fluorine-containing compound (A)”). )) In the crude HFO-1234yf, it can be further increased by HFO-1234yf / fluorine-containing compound (A).
  • the purified HFO-1234yf in this specification is related to the crude HFO-1234yf described below, and the HFO-1234yf / fluorine-containing compound (A) in the resulting purified HFO-1234yf used the crude HFO-1234yf used. It means a mixture containing HFO-1234yf or a pure HFO-1234yf product, which is higher than HFO-1234yf / fluorinated compound (A) at ⁇ 1234yf.
  • the crude HFO-1234yf when the crude HFO-1234yf contains R40, the crude HFO-1234yf is directly used as a composition for distillation, or when the crude HFO-1234yf does not contain R40, the crude HFO-1234yf is used.
  • R40 By adding R40 to the composition for distillation, azeotropic distillation based on azeotropic distillation of HFO-1234yf and R40 can be performed.
  • the HFO-1234yf / fluorine-containing compound (A) in the distillation composition is equal to that in the crude HFO-1234yf.
  • HFO-1234yf / fluorine-containing compound (A) in purified HFO-1234yf can be higher than HFO-1234yf / fluorine-containing compound (A) in the composition for distillation.
  • purified HFO-1234yf can be efficiently obtained from a mixture containing HFO-1234yf and the fluorine-containing compound (A).
  • HFO-1234yf and R40 azeotrope it has not been known so far that HFO-1234yf and R40 azeotrope, and the present inventors have newly found out and applied to the purification method of the present invention. That is, the present inventors searched for a compound that azeotropes with HFO-1234yf instead of hydrogen fluoride, which is difficult to handle due to the load on the equipment and the like, and has a low load on the equipment and the like and is easy to handle. .
  • R40 to be present in a mixture containing a compound having a boiling point close to that of HFO-1234yf and HFO-1234yf, that is, if the mixture contains R40, this is left as it is, and if it does not contain R40, R40 is added to perform distillation.
  • the azeotropic composition or azeotrope-like composition of HFO-1234yf and R40 will be described.
  • 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 depending on the pressure conditions.
  • the azeotropic composition of HFO-1234yf and R40 is a composition in which the relative volatility represented by the following formula (1) is 1.00 under the condition of a gauge pressure of 0.5 MPa, and is obtained as follows. .
  • the boiling point of the azeotropic composition of HFO-1234yf and R40 is 18.0 ° C. at the pressure gauge pressure of 0.5 MPa.
  • a mixture of HFO-1234yf and R40 having a predetermined composition is put into a 500 mL autoclave equipped with a pressure gauge and gradually heated by an external heater so that the pressure becomes 0.5 MPa as a gauge pressure. After the pressure in the autoclave has reached 0.5 MPa as a gauge pressure, the composition in the autoclave is stabilized for a certain period of time, and then a sample is taken from the gas phase and the liquid phase. HFO-1234yf and R40 in the gas phase and liquid phase samples are analyzed by gas chromatography to obtain the composition of HFO-1234yf and R40 in each sample. The obtained composition is inserted into the above formula (1) to determine the relative volatility.
  • This operation is performed by changing the composition of HFO-1234yf and R40 in the mixture charged in the autoclave to obtain a composition having a relative volatility of 1.00, and an azeotropic composition at a gauge pressure of 0.5 MPa is obtained.
  • the azeotropic composition of HFO-1234yf and R40 at normal pressure is determined based on the experimental value of the azeotropic composition obtained above and the simulation using the known thermodynamic characteristics / calculated thermodynamic characteristics. It is calculated that the content ratio of 1234yf is 57 mol% and the content ratio of R40 is 43 mol%. Further, the boiling point of the azeotropic composition of HFO-1234yf and R40 can be calculated as ⁇ 32 ° C. at normal pressure.
  • a composition having a composition close to the azeotropic composition is an azeotropic-like composition that exhibits behavior close to azeotropic. That is, an azeotrope-like composition has a tendency not to fractionate when evaporated or condensed, and the composition of the gas phase produced by vaporization of the liquid phase is different from the composition of the vapor phase to be vaporized or 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 HFO-1234yf and R40 is a range in which the composition is distilled and / or refluxed with little compositional change under normal distillation conditions.
  • the composition range in which the composition is distilled and / or refluxed with little compositional change can be defined, for example, as a range in which the relative volatility at a predetermined pressure is 1.00 ⁇ ⁇ .
  • the composition range of the azeotrope-like composition of HFO-1234yf and R40 is preferably a range in which the relative volatility is 1.00 ⁇ 0.20 at a predetermined pressure.
  • a predetermined pressure for example, at a gauge pressure of 0.5 MPa
  • the composition range of HFO-1234yf and R40 having a relative volatility of 1.00 ⁇ 0.20 is the same as that for obtaining the azeotropic composition described above. It can be obtained by measuring the mol% of both compounds in the gas phase and liquid phase while gradually changing the composition of HFO-1234yf and R40 under the condition of a pressure of 0.5 MPa.
  • the composition of the azeotrope-like composition of HFO-1234yf and R40 having a relative volatility in the range of 1.00 ⁇ 0.20 at a gauge pressure of 0.5 MPa, obtained by such a method, is HFO-1234yf with respect to R40.
  • the molar ratio is 41/59 to 85/15 (hereinafter also referred to as “HFO-1234yf / R40”).
  • the azeotrope-like composition comprising HFO-1234yf and R40 in the above composition range has a boiling point of 18 to 19 ° C. under the condition that the pressure is a gauge pressure of 0.5 MPa.
  • composition range of the azeotrope-like composition of HFO-1234yf and R40 in the range where the relative volatility at normal pressure is 1.00 ⁇ 0.20 is the azeotrope at the gauge pressure of 0.5 MPa obtained above.
  • the range of HFO-1234yf / R40 on the liquid phase side is calculated to be 46/54 to 73/27 by simulation using experimental values of the composition of the like composition and known thermodynamic characteristics / calculated thermodynamic characteristics.
  • the boiling point of an azeotrope-like composition comprising HFO-1234yf and R40 in the above composition range can be calculated as ⁇ 31 to ⁇ 32 ° C. at normal pressure.
  • azeotropic composition of HFO-1234yf and R40 and the composition range of the azeotrope-like composition were calculated by simulation using known thermodynamic characteristics and calculated thermodynamic characteristics at various pressures (gauge pressures). The results are shown in Table 1 together with the results of normal pressure and gauge pressure of 0.5 MPa.
  • an azeotrope-like composition can be handled substantially equivalent to said azeotrope composition.
  • an azeotrope-like composition is described as including an azeotrope composition.
  • step is a step of preparing a distillation composition containing the fluorine-containing compound (A), HFO-1234yf, and R40.
  • the purification method of the present invention can target crude HFO-1234yf containing at least the fluorine-containing compound (A) and HFO-1234yf.
  • the purification method of the present invention is a method for obtaining purified HFO-1234yf in which the ratio of the fluorine-containing compound (A) to HFO-1234yf is reduced compared to crude HFO-1234yf to be purified.
  • the fluorine-containing compound (A) is a fluorine-containing compound having a boiling point of ⁇ 14 to ⁇ 30 ° C. (excluding HFO-1234yf), and is used, for example, when HFO-1234yf is produced by a conventionally known production method Unreacted raw materials, intermediates produced during the production process, by-products and the like. Further, as the crude HFO-1234yf containing the fluorine-containing compound (A) and HFO-1234yf, specifically, a reaction product obtained by producing HFO-1234yf by a conventionally known production method, or a conventional method And a crude product purified by 1).
  • fluorine-containing compound (A) examples include 3,3-difluoropropene (HFO-1252zf), dichlorodifluoromethane (CFC-12), and hexafluoropropene (HFP) whose boiling points are shown in Table 2.
  • Chlorotrifluoroethylene CFE
  • hexafluoroacetone hexafluoropropylene oxide
  • HFPO 1,1,1,2-tetrafluoroethane
  • HFC-134a 1,2-difluoroethylene (Z) (HFO— 1132 (Z))
  • 1-chloro-1-fluoroethylene HCFO-1131a
  • 3,3,3-trifluoropropene HFO-1243zf
  • 1,1-difluoroethane HFC-152a
  • 1-chloro- 1-fluoroethane HFC-151a
  • 1-fluoropropene Z / E) HFC-1261ze (Z / E)
  • 2-fluoropropene HFC-1261yf
  • 1,1,2,2-tetrafluoroethane HFC-134
  • 1,1,2,3, 3-pentafluoropropene HFO-1225yc
  • 1,1,3,3,3-pentafluoropropene HFO-1225
  • the fluorine-containing compound (A) has a boiling point of ⁇ 14 to ⁇ 30 ° C. as shown in Table 2, the difference in boiling point between the boiling point range of the azeotrope-like composition of HFO-1234yf and R40 is sufficient. Fractionation of 1234yf with an azeotrope-like composition of R40 is possible. In addition, the fluorine-containing compound (A) is close to the boiling point of HFO-1234yf ( ⁇ 29 ° C.) to the extent that it cannot be easily separated by ordinary distillation, and is advantageous in terms of purification efficiency.
  • the fluorine-containing compound (A) in the case of the fluorine-containing compound (A) having a boiling point of ⁇ 19 to ⁇ 30 ° C., the effect relating to the purification efficiency in the method of the present invention is more remarkable. In the case of the fluorine-containing compound (A) at -28 ° C., the effect on the purification efficiency in the method of the present invention is particularly remarkable.
  • Examples of such compounds include diazomethane (CH 2 —N 2 , ⁇ 23 ° C.), dimethylsilane (CH 3 —SiH 2 —CH 3 , ⁇ 22 ° C.), dicyan (NC—CN, ⁇ 21 ° C.), and ethynylmethyl.
  • Ether CH ⁇ C—O—CH 3 , ⁇ 17 ° C.
  • vinyl chloride CH 2 ⁇ CHCl, ⁇ 14 ° C.
  • chloroacetylene Cl—C ⁇ C—H, ⁇ 30 ° C.
  • dimethyl ether CH 3 — O—CH 3 , ⁇ 24 ° C.
  • formaldehyde HC (O) —H, ⁇ 19 ° C.
  • HFO-1234yf contains a compound having a boiling point exceeding ⁇ 14 ° C. in addition to the compound having a boiling point of ⁇ 14 ° C. to ⁇ 30 ° C., these compounds are also subjected to the purification method of the present invention. And HFO-1234yf can be separated.
  • HFO-1243zf is said to azeotrope with HFO-1234yf, and the boiling point of the azeotrope-like composition is about ⁇ 14 psia to about 230 psia (about 0.1 MPa to about 1.6 MPa). 30 ° C to about 66 ° C.
  • HFO-1234yf and R40 form an azeotrope-like composition and are contained by ordinary distillation. Since it is fractionated as a fraction, HFO-1234yf and HFO-1243zf can be easily separated. This is because the boiling point of the azeotrope-like composition of HFO-1234yf and R40 is lower than the boiling point of the azeotrope-like composition of HFO-1234yf and HFO-1243zf.
  • preparing the distillation composition in the step (a) means that, for example, in the crude HFO-1234yf obtained in the process of producing HFO-1234yf as described above, the crude HFO-1234yf contains R40. Includes using the crude HFO-1234yf as it is as a composition for distillation. Similarly, when the crude HFO-1234yf does not contain R40, a composition for distillation is prepared by adding R40 to the crude HFO-1234yf.
  • each of the fluorine-containing compound (A), HFO-1234yf and R40 contained in the distillation composition prepared in the step (a) are not particularly limited.
  • an azeotrope-like composition of HFO-1234yf and R40 is formed from the distillation composition by distillation in step (b), and fractionated as a fraction containing this.
  • the azeotrope-like composition can be formed regardless of the proportion of HFO-1234yf and R40 contained in the distillation composition. Therefore, the contents of HFO-1234yf and R40 in the distillation composition prepared in step (a) are not particularly limited.
  • substantially the entire amount of HFO-1234yf in the distillation composition in step (b) is used as a fraction containing the azeotrope-like composition. It is preferable to carry out fractional distillation.
  • HFO-1234yf / R40 in the composition for distillation is preferably not more than the upper limit of HFO-1234yf / R40 of the azeotrope-like composition at a predetermined distillation pressure, and HFO-1234yf / R40 of the azeotrope composition. R40 or less is more preferable. If HFO-1234yf / R40 is less than or equal to the upper limit of HFO-1234yf / R40 of the azeotrope-like composition at the pressure, substantially the entire amount of HFO-1234yf in the distillation composition in the ordinary distillation Can be fractionated as fractions containing
  • HFO-1234yf / R40 is equal to or lower than HFO-1234yf / R40 of the azeotropic composition, it is possible to more efficiently separate HFO-1234yf in the distillation composition from the fraction containing the azeotropic-like composition. it can.
  • the upper limit value 99/1 of HFO-1234yf / R40 forming the azeotrope-like composition is a value when the pressure is 1.3 to 3.0 MPaG. In the case of 5 MPaG, the upper limit of HFO-1234yf / R40 forming the azeotrope-like composition is 85/15, and 73/27 at normal pressure.
  • the upper limit value of HFO-1234yf / R40 that forms an azeotrope-like composition at a possible set pressure is calculated and used for distillation. It is preferable to adjust so that HFO-1234yf / R40 in the composition is less than or equal to this upper limit value.
  • the pressure range in which distillation is performed is usually about 0 to 3.0 MPa in gauge pressure (hereinafter, when the pressure is gauge pressure, “G” is added after the unit). Further, as shown in Table 1, the composition range in which the azeotrope-like composition is formed in the pressure range of 0 to 3.0 MPaG is 26/74 to 99/1 as HFO-1234yf / R40. The composition range in which the product is formed is 57/43 (about 1.33).
  • the amount of R40 in the composition for distillation is preferably 0.01 mol or more, more preferably 0.1 mol or more, and more preferably 0.2 mol or more with respect to 1 mol of HFO-1234yf. Is more preferably 0.5 mol or more, and most preferably 0.75 mol or more.
  • surplus HFO-1234yf that does not form an azeotrope-like composition is fractionated into a fraction (usually a fraction containing a fluorine-containing compound (A)) different from the fraction containing the azeotrope-like composition. The loss of HFO-1234yf due to this can be suppressed.
  • the amount of R40 in the distillation composition may be set larger than the above value.
  • the amount of R40 in the distillation composition is HFO.
  • the amount is preferably 100 mol or less, more preferably 10 mol or less, with respect to 1 mol of ⁇ 1234yf.
  • the composition for distillation measures for example, the contents of HFO-1234yf and R40 for the crude HFO-1234yf to which the purification method of the present invention is applied, and according to these contents
  • the resulting composition for distillation can be prepared by adding or not adding R40 to the crude HFO-1234yf such that HFO-1234yf / R40 is in the above-mentioned preferred range.
  • the crude HFO-1234yf used in the present invention contains R40 in excess exceeding the composition range of the azeotrope-like composition, which is the preferred range, the crude HFO-1234yf is used as it is as a composition for distillation.
  • the distillation composition is not necessarily composed only of HFO-1234yf, the fluorine-containing compound (A) and R40. As long as the effects of the present invention are not impaired, compounds other than HFO-1234yf, the fluorine-containing compound (A) and R40 may be contained. These compounds are usually compounds brought into the distillation composition in the form contained in the crude HFO-1234yf.
  • Crude HFO-1234yf to which the purification method of the present invention is applied is, for example, R40 and a fluorine-containing compound that can be thermally decomposed to generate F 2 C :, for example, R22, tetrafluoroethylene (TFE), HFP, From a reaction product obtained by a synthesis method of HFO-1234yf accompanied by thermal decomposition with octafluorocyclobutane (RC318), CTFE, trifluoroethylene (HFO-1123), hexafluoropropylene oxide (HFPO), etc., by distillation or the like It can be obtained by fractionating a fraction comprising a mixture of HFO-1234yf, fluorine-containing compound (A) and R40 or a fraction comprising the mixture as a main component.
  • TFE tetrafluoroethylene
  • the crude HFO-1234yf obtained by the method for synthesizing HFO-1234yf accompanied by thermal decomposition can contain all of the fluorine-containing compound (A) shown in Table 1 above.
  • the crude HFO-1234yf thus obtained is used as a composition for distillation as it is or with the addition of R40, other compounds other than HFO-1234yf, fluorine-containing compound (A) and R40 as described above May be contained within a range not impairing the effects of the present invention.
  • the content of other compounds in the distillation composition is preferably less than 90 mol%, more preferably less than 70 mol%.
  • Many of the other compounds are compounds having a large difference in boiling point from HFO-1234yf and the fluorine-containing compound (A), and can be easily separated by ordinary distillation before carrying out the purification method of the present invention.
  • Crude HFO-1234yf applicable to the purification method of the present invention includes, in addition to the above, for example, crude HFO obtained when HFO-1234yf is produced using an isomer mixture of dichloropentafluoropropane (HCFC-225). -1234yf.
  • crude HFO-1234yf contains 2,2-dichloro-1,1,3,3, in the raw material composition as a fluorine-containing compound (A).
  • reaction product containing unreacted raw materials obtained when HFO-1234yf is produced by dehydrofluorinating HFC-245cb described in Patent Document 3 is a crude product applicable to the purification method of the present invention.
  • HFO-1234yf the fluorine-containing compound (A) contained in the crude HFO-1234yf can contain HFC-245cb and the like.
  • the crude HFO-1234yf when these crude HFO-1234yf is applied to the purification method of the present invention, since the crude HFO-1234yf basically does not contain R40, a predetermined amount of R40 is added in step (a) to add a composition for distillation.
  • the crude HFO-1234yf used may contain other compounds other than HFO-1234yf, the fluorine-containing compound (A) and R40 in the same manner as the crude HFO-1234yf obtained by the method for synthesizing HFO-1234yf accompanied by thermal decomposition. Good.
  • the content of other compounds is preferably less than 90 mol% and more preferably less than 70 mol% as the content when the composition for distillation is used.
  • step (B) Azeotropic distillation step
  • the distillation composition prepared in the above step (a) is obtained by dividing a fraction containing an azeotrope-like composition of HFO-1234yf and R40. It is the process used for the formed distillation.
  • Distillation in the step (b) is to prepare the distillation composition in the step (a) as described above, so that no special conditions are required.
  • the pressure condition is preferably 0 (normal pressure) to 2.0 MPaG, and the temperature condition is preferably ⁇ 32 to 68 ° C. as the tower top temperature depending on the set pressure.
  • the fraction containing the azeotrope-like composition of HFO-1234yf and R40 may be referred to as an azeotropic fraction.
  • the distillation in the step (b) is preferably carried out so that the ratio of the amount of HFO-1234yf in the azeotropic fraction to the amount of HFO-1234yf in the distillation composition is 75 mol% or more, and 85 mol% The above is more preferable, 95 mol% or more is further preferable, and 99 mol% or more is most preferable.
  • the distillation is preferably performed so that the ratio of the amount of the fluorine-containing compound (A) in the azeotropic fraction to the amount of the fluorine-containing compound (A) in the distillation composition is 50 mol% or less, 25 The mol% or less is more preferable, the 15 mol% or less is more preferable, and the 5 mol% or less is most preferable. Thereby, higher purity HFO-1234yf 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 set to the fluorine-containing compound It is preferable to make it below the boiling point of (A). This is mainly done by adjusting the tower top temperature.
  • the reboiler load can be reduced by reducing the difference between the tower top temperature and the tower bottom temperature.
  • 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, generally from -15 to 50 ° C.
  • Such pressure is preferably 0.1 to 1.3 MPaG.
  • the distillation in the step (b) includes, for example, a distillation column, a means for supplying a distillation composition to the distillation tower, a means for taking a distillate from the top of the distillation tower, and a bottom of the distillation tower. It can carry out using the distillation apparatus provided with the means to take out bottoms.
  • the distillation column used may be a hollow distillation column or a multistage distillation column. Moreover, distillation may be performed batchwise or continuously.
  • the distillation composition When distillation is performed using, for example, a multi-stage distillation column, the distillation composition is usually supplied from the middle stage of the distillation column, and the azeotropic fraction is obtained as a distillate from the top of the distillation column. .
  • a fraction containing the fluorine-containing compound (A) contained in the distillation composition (hereinafter also referred to as a fluorine-containing compound (A) fraction) can be collected as a bottoms from the tower bottom. .
  • the fractionation of the azeotropic fraction as the distillate is not limited to fractionation from the top of the column, but from the stage where the composition for distillation is fed into the column.
  • An azeotropic distillate can be taken out as a distillate from any stage in the upper stage.
  • the present invention describes an embodiment in which the fluorine-containing compound (A) fraction is taken out from the bottom of the column as a bottoms.
  • the present invention is not limited to this, and a distillation composition is supplied into the column. If it is a stage below the stage to perform, a fluorine-containing compound (A) fraction can be taken out as a bottoms.
  • the boiling point of the azeotrope-like composition of HFO-1234yf and R40 at normal pressure is ⁇ 31 to ⁇ 32 ° C.
  • the boiling point of the fluorine-containing compound (A) is ⁇ 14 to ⁇ 30. This is because the boiling point of HFO-1234yf is -29 ° C and the boiling point of R40 is -24.2 ° C.
  • HFO-1234yf When HFO-1234yf is contained in the fluorine-containing compound (A) fraction, HFO-1234yf is separated from the fluorine-containing compound (A) fraction by further performing the steps (a) and (b). .
  • R40 When R40 is contained in the fluorine-containing compound (A) fraction, in the above step (a), this is added to the crude HFO-1234yf to prepare a composition for distillation, and then subjected to step (b). R40 may be separated from the fluorine-containing compound (A) fraction.
  • step (a) HFO-1234yf / R40 in the composition for distillation is adjusted to the composition of the azeotrope-like composition under predetermined distillation conditions, and distillation is performed under the predetermined distillation conditions in step (b).
  • step (b) By carrying out, it becomes possible to fractionate into an azeotropic fraction containing an azeotrope-like composition of HFO-1234yf and R40 and a fluorinated compound (A) fraction substantially free of HFO-1234yf and R40.
  • the azeotropic fraction obtained in the step (b) is supplied to the next step (c) to concentrate HFO-1234yf.
  • the content ratio of compounds other than HFO-1234yf and R40 in the azeotropic fraction is 90% by mass or less, preferably 70% by mass or less, and more preferably 50% by mass or less with respect to the total amount of the azeotropic fraction.
  • the purified HFO-1234yf obtained has a higher HFO-1234yf / fluorine-containing compound (A) as defined above than HFO-1234yf / fluorine-containing compound (A) in the crude HFO-1234yf used. Is.
  • HFO-1234yf / R40 in the azeotropic fraction obtained in the step (b) is in the range of 26/74 to 99/1.
  • the content of HFO-1234yf in the purified HFO-1234yf obtained in this step (c) is preferably 90% by mass or more, more preferably 95% by mass or more, and more preferably 99% by mass or more based on the total amount of the purified HFO-1234yf. Further preferred.
  • step (C) As a specific method of the step (c), at least one separation method selected from swing distillation, extractive distillation, azeotropic distillation, phase separation and membrane separation is applicable. These separation methods are general methods used when separating an azeotropic composition into constituent compounds. When the azeotropic fraction obtained in step (b) is subjected to these separation methods, it is usually used. Just follow the law.
  • Examples 1 to 6 are examples, and Examples 7 and 9 are comparative examples. The present invention is not limited to these examples.
  • Example 7 In Examples 1 to 6, the distillation compositions shown in Tables 3 to 8 including HFO-1234yf, HFO-1243zf, and R40, respectively, are prepared as distillation compositions. In Example 7, the distillation composition shown in Table 9 containing only HFO-1234yf and HFO-1243zf as the distillation composition is prepared. In Examples 1 to 7, these distillation compositions were supplied from the top of a distillation column having a theoretical plate number of 50 to the distillation column at a flow rate of 1.0 mol / hr from the 40th column. Continuous distillation is carried out at the operating pressure [MPaG], tower top temperature [° C.] and tower bottom temperature [° C.] shown in FIG.
  • MPaG operating pressure
  • Example 1 to 7 the distillate is withdrawn from the top of the column and the bottoms are withdrawn from the bottom of the column at the speeds shown in Tables 3 to 9 (total amount [mol / H]).
  • Tables 3 to 9 total amount [mol / H]).
  • the composition of each of the extracted distillate and bottoms is analyzed by gas chromatography.
  • the analysis results of the composition of the distillate and bottoms in Examples 1 to 7 are shown in Tables 3 to 9 below.
  • the recoveries from the distillation composition in the distillate and the bottoms for each component in the distillation composition in Examples 1 to 7 were determined by the following equations.
  • Recovery rate (%) component amount in distillate or bottoms / component amount in distillation composition ⁇ 100
  • the ratio (mol%) of HFO-1234yf to the total amount of HFO-1234yf and HFO-1243zf in the distillation composition, distillate and bottoms was determined.
  • the ratio (mol%) of the total amount of HFO-1234yf and R40 to the total amount in the distillation composition, distillate and bottoms was determined.
  • HFO-1234yf / R40 (molar ratio) in the distillation composition, distillate and bottoms was determined. The results in each example are shown in the lower column of Tables 3 to 9.
  • the distillates obtained in Examples 1 to 6 contain an azeotrope-like composition of HFO-1234yf and R40, the total content of which is 95.96 to 99.77 mol%, and HFO-1243zf Is a well-removed mixture. From such a distillate, R40 is mainly removed by at least one separation method selected from swing distillation, extractive distillation, azeotropic distillation, phase separation and membrane separation to obtain purified HFO-1234yf.
  • Example 8 the distillation composition shown in Table 10 containing HFO-1234yf, HFC-152a and R40 is prepared as the distillation composition.
  • Example 9 the distillation composition shown in Table 11 containing only HFO-1234yf and HFC-152a is prepared as the distillation composition.
  • these distillation compositions were fed from the top of a distillation column having 50 theoretical plates to the distillation column at a flow rate of 1.0 mol / hr from the 40th column. Are continuously distilled at an operating pressure [MPaG], a column top temperature [° C.], and a column bottom temperature [° C.].
  • Example 8 and 9 the distillate is extracted from the top of the column at the speeds shown in Tables 10 and 11 (total amount [mol / H]), and the bottom is extracted from the bottom.
  • Tables 10 and 11 total amount [mol / H]
  • Tables 10 and 11 total amount [mol / H]
  • the recoveries from the distillation composition in the distillate and the bottoms were determined in the same manner as in Example 1 above for each component in the distillation composition in Examples 8 and 9. Further, the ratio (mol%) of HFO-1234yf to the total amount of HFO-1234yf and HFC-152a in the distillation composition, distillate and bottoms was determined. The ratio (mol%) of the total amount of HFO-1234yf and R40 to the total amount in the distillation composition, distillate and bottoms was determined. HFO-1234yf / R40 (molar ratio) in the distillation composition, distillate and bottoms was determined. The results in each example are shown in the lower columns of Tables 10 and 11.
  • the distillate obtained in Example 8 contains an azeotrope-like composition of HFO-1234yf and R40, the content of which is 99.40 mol%, and is a mixture from which HFC-152a is well removed. .
  • R40 is mainly removed by at least one separation method selected from swing distillation, extractive distillation, azeotropic distillation, phase separation and membrane separation to obtain purified HFO-1234yf.
  • Example 10 As the distillation composition, there are prepared HFO-1234yf, various fluorine-containing compounds (A) shown in Table 12, and a distillation composition shown in Table 12 containing R40. This distillation composition was supplied to the distillation column at a flow rate of 1.0 mol / hr from the 40th stage from the top of the distillation tower having a theoretical plate number of 50, and the operating pressure [MPaG] shown in Table 12 was Continuous distillation is performed at the top temperature [° C.] and the bottom temperature [° C.].
  • the distillate is withdrawn from the top of the column at the rate shown in Table 12 (total amount recovered [mol / H]), and the bottom is withdrawn from the bottom.
  • Table 12 total amount recovered [mol / H]
  • the composition of each of the extracted distillate and bottoms is analyzed by gas chromatography. The analysis results of the composition of the distillate and the bottoms in Example 10 are shown in Table 12 below.
  • the recovery rate from the distillation composition in the distillate and the bottoms was determined in the same manner as in Example 1 for each component in the distillation composition in Example 10. Further, the ratio (mol%) of HFO-1234yf to the total amount of HFO-1234yf and the fluorine-containing compound (A) in the distillation composition, distillate and bottoms was determined. The ratio (mol%) of the total amount of HFO-1234yf and R40 to the total amount in the distillation composition, distillate and bottoms was determined. HFO-1234yf / R40 (molar ratio) in the distillation composition, distillate and bottoms was determined. The results are shown in the lower column of Table 12.
  • the distillate obtained in Example 10 contained an azeotrope-like composition of HFO-1234yf and R40, the content of which was 99.74 mol%, and the fluorine-containing compound (A) was well removed. It is a mixture. From such a distillate, R40 is mainly removed by at least one separation method selected from swing distillation, extractive distillation, azeotropic distillation, phase separation and membrane separation to obtain purified HFO-1234yf.
  • HFO-1234yf can be efficiently purified from a mixture containing HFO-1234yf and a fluorine-containing compound having a boiling point close to that of HFO-1234yf. It is effectively used to obtain high-purity HFO-1234yf from HFO-1234yf.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé de purification efficace de 2,3,3,3-tétrafluoropropène (HFO-1234yf) à partir d'un mélange qui contient du HFO-1234yf et un composé de fluor, dont le point d'ébullition est proche de celui du HFO-1234yf. Ce procédé de purification de HFO-1234yf comprend : (a) une étape de préparation d'une composition de distillation qui contient un composé de fluor (à l'exclusion du HFO-1234yf), dont le point d'ébullition est compris entre -14°C et -30°C inclus, du HFO-1234yf, et du chlorométhane; (b) une étape de soumission de la composition de distillation à une distillation dans laquelle une composition azéotropique de HFO-1234yf et de chlorométhane, et une fraction contenant une composition pseudo-azéotrope sont formées; et (c) une étape d'obtention, à partir de ladite fraction, de HFO-1234yf purifié ayant une concentration plus élevée en HFO-1234yf que ladite fraction.
PCT/JP2014/076995 2013-10-09 2014-10-08 Procédé de purification de 2,3,3,3-tétrafluoropropène WO2015053339A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2015541622A JP6358263B2 (ja) 2013-10-09 2014-10-08 ２，３，３，３−テトラフルオロプロペンの精製方法
CN201480055614.8A CN105612139B (zh) 2013-10-09 2014-10-08 2,3,3,3‑四氟丙烯的纯化方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-211748 2013-10-09
JP2013211748 2013-10-09

Publications (1)

Publication Number Publication Date
WO2015053339A1 true WO2015053339A1 (fr) 2015-04-16

Family

ID=52813154

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/076995 WO2015053339A1 (fr) 2013-10-09 2014-10-08 Procédé de purification de 2,3,3,3-tétrafluoropropène

Country Status (3)

Country Link
JP (1) JP6358263B2 (fr)
CN (1) CN105612139B (fr)
WO (1) WO2015053339A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2939994A4 (fr) * 2012-12-27 2016-08-03 Asahi Glass Co Ltd Procédé pour la purification de tétrafluoropropène
WO2016194403A1 (fr) * 2015-05-29 2016-12-08 ダイキン工業株式会社 Procédé de production d'un composé contenant du fluor
WO2017122222A1 (fr) 2016-01-14 2017-07-20 Srf Limited Procédé pour la préparation d'oléfine contenant du fluor
US9892932B2 (en) 2014-06-18 2018-02-13 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Chemistries for TSV/MEMS/power device etching
CN108368007A (zh) * 2015-12-23 2018-08-03 阿科玛法国公司 生产和纯化2,3,3,3-四氟-1-丙烯的方法
WO2019075212A1 (fr) * 2017-10-13 2019-04-18 Honeywell International Inc. Procédé d'élimination des impuretés halogénées insaturées du 2,3,3,3-tétrafluoropropène (hfo-1234yf)
WO2019220454A1 (fr) * 2018-05-16 2019-11-21 Srf Limited Procédé de purification d'une charge oléfinique comprenant 1234 yf
WO2021158837A3 (fr) * 2020-02-07 2021-09-23 The Chemours Company Fc, Llc Compositions comprenant du 2,3,3,3-tétrafluoropropène et leurs procédés de fabrication et d'utilisation

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111253211B (zh) * 2020-03-16 2022-08-05 天津绿菱气体有限公司 一种高纯电子级四氟丙烯HFO-1234yf的分离纯化方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2931840A (en) * 1958-11-25 1960-04-05 Du Pont Process for preparing 2, 3, 3, 3-tetrafluoropropene
JP2008506793A (ja) * 2004-04-16 2008-03-06 ハネウェル・インターナショナル・インコーポレーテッド テトラフルオロフ゜ロヘ゜ンとトリフルオロヨート゛メタンとの共沸性組成物
WO2011030026A1 (fr) * 2009-09-11 2011-03-17 Arkema France Fluide refrigerant binaire
CN102442880A (zh) * 2011-10-22 2012-05-09 山东东岳高分子材料有限公司 一种2,3,3,3-四氟丙烯的制备方法
JP5149456B1 (ja) * 2012-03-14 2013-02-20 旭硝子株式会社 ２，３，３，３−テトラフルオロプロペンおよび１，１−ジフルオロエチレンの製造方法
WO2013154059A1 (fr) * 2012-04-09 2013-10-17 旭硝子株式会社 Composition azéotropique ou de type azéotrope, et procédé de production de 2,3,3,3-tétrafluoropropène ou de chlorométhane

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7074751B2 (en) * 2004-04-16 2006-07-11 Honeywell International Inc. Azeotrope-like compositions of tetrafluoropropene and trifluoroiodomethane
CN106146246A (zh) * 2011-02-04 2016-11-23 旭硝子株式会社 2,3,3,3‑四氟丙烯的纯化方法
JP5201284B1 (ja) * 2012-03-14 2013-06-05 旭硝子株式会社 ２，３，３，３−テトラフルオロプロペンの製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2931840A (en) * 1958-11-25 1960-04-05 Du Pont Process for preparing 2, 3, 3, 3-tetrafluoropropene
JP2008506793A (ja) * 2004-04-16 2008-03-06 ハネウェル・インターナショナル・インコーポレーテッド テトラフルオロフ゜ロヘ゜ンとトリフルオロヨート゛メタンとの共沸性組成物
WO2011030026A1 (fr) * 2009-09-11 2011-03-17 Arkema France Fluide refrigerant binaire
CN102442880A (zh) * 2011-10-22 2012-05-09 山东东岳高分子材料有限公司 一种2,3,3,3-四氟丙烯的制备方法
JP5149456B1 (ja) * 2012-03-14 2013-02-20 旭硝子株式会社 ２，３，３，３−テトラフルオロプロペンおよび１，１−ジフルオロエチレンの製造方法
WO2013154059A1 (fr) * 2012-04-09 2013-10-17 旭硝子株式会社 Composition azéotropique ou de type azéotrope, et procédé de production de 2,3,3,3-tétrafluoropropène ou de chlorométhane

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2939994A4 (fr) * 2012-12-27 2016-08-03 Asahi Glass Co Ltd Procédé pour la purification de tétrafluoropropène
US10720335B2 (en) 2014-06-18 2020-07-21 American Air Liquide, Inc. Chemistries for TSV/MEMS/power device etching
US9892932B2 (en) 2014-06-18 2018-02-13 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Chemistries for TSV/MEMS/power device etching
US10103031B2 (en) 2014-06-18 2018-10-16 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Georges Claude Chemistries for TSV/MEMS/power device etching
WO2016194403A1 (fr) * 2015-05-29 2016-12-08 ダイキン工業株式会社 Procédé de production d'un composé contenant du fluor
JP2016222603A (ja) * 2015-05-29 2016-12-28 ダイキン工業株式会社 含フッ素化合物の製造方法
CN108368007A (zh) * 2015-12-23 2018-08-03 阿科玛法国公司 生产和纯化2,3,3,3-四氟-1-丙烯的方法
JP2018538316A (ja) * 2015-12-23 2018-12-27 アルケマ フランス ２，３，３，３−テトラフルオロ−１−プロペンを製造及び精製するための方法
WO2017122222A1 (fr) 2016-01-14 2017-07-20 Srf Limited Procédé pour la préparation d'oléfine contenant du fluor
US10239804B2 (en) 2016-01-14 2019-03-26 Srf Limited Process for the preparation of 2,3,3,3-tetrafluoropropene from methyl chloride and chlorodifluoromethane
WO2019075212A1 (fr) * 2017-10-13 2019-04-18 Honeywell International Inc. Procédé d'élimination des impuretés halogénées insaturées du 2,3,3,3-tétrafluoropropène (hfo-1234yf)
WO2019220454A1 (fr) * 2018-05-16 2019-11-21 Srf Limited Procédé de purification d'une charge oléfinique comprenant 1234 yf
US11225447B2 (en) 2018-05-16 2022-01-18 Srf Limited Process for purification of olefin feed comprising 1234YF
WO2021158837A3 (fr) * 2020-02-07 2021-09-23 The Chemours Company Fc, Llc Compositions comprenant du 2,3,3,3-tétrafluoropropène et leurs procédés de fabrication et d'utilisation

Also Published As

Publication number Publication date
CN105612139B (zh) 2017-09-19
JP6358263B2 (ja) 2018-07-18
CN105612139A (zh) 2016-05-25
JPWO2015053339A1 (ja) 2017-03-09

Similar Documents

Publication Publication Date Title
JP6358263B2 (ja) ２，３，３，３−テトラフルオロプロペンの精製方法
KR102035526B1 (ko) 3,3,3-트라이플루오로프로펜 및 플루오르화수소를 포함하는 공비 조성물 및 이의 분리방법
EP2247560B1 (fr) Procédés de séparation de 1,3,3,3-tétrafluoropropène de fluorure d'hydrogène par distillation azéotropique
KR101946378B1 (ko) 공비 증류에 의한 플루오르화수소로부터의 2,3,3,3-테트라플루오로프로펜의 분리 방법
JP6613877B2 (ja) 共沸様組成物および精製された含フッ素化合物の製造方法
JP6102917B2 (ja) 共沸または共沸様組成物、および２，３，３，３−テトラフルオロプロペンまたはクロロメタンの製造方法
EP3345888B1 (fr) Procédés de distillation extractive pour séparer de l'e-1,2,3,3,3-pentafluoropropène du z-1,2,3,3,3-pentafluoropropène
JP6011008B2 (ja) 共沸または共沸様組成物、および２，３，３，３−テトラフルオロプロペンまたはヘキサフルオロプロペンの製造方法
WO2015045927A1 (fr) Procédé de séparation d'hexafluoropropène d'un composé fluoré
JP2013230998A (ja) 共沸または共沸様組成物、およびクロロメタンまたはヘキサフルオロプロペンの製造方法
JP2013230997A (ja) 共沸または共沸様組成物、およびクロロメタンまたはクロロトリフルオロエチレンの製造方法
JP2013230996A (ja) 共沸または共沸様組成物、および２，３，３，３−テトラフルオロプロペンまたはクロロトリフルオロエチレンの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14851836

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015541622

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14851836

Country of ref document: EP

Kind code of ref document: A1