WO2019208546A1 - Procédé de production d'un hydrocarbure insaturé contenant du fluor - Google Patents

Procédé de production d'un hydrocarbure insaturé contenant du fluor Download PDF

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WO2019208546A1
WO2019208546A1 PCT/JP2019/017160 JP2019017160W WO2019208546A1 WO 2019208546 A1 WO2019208546 A1 WO 2019208546A1 JP 2019017160 W JP2019017160 W JP 2019017160W WO 2019208546 A1 WO2019208546 A1 WO 2019208546A1
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fluorine
reaction
aqueous solution
production method
compound
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PCT/JP2019/017160
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Japanese (ja)
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真理 市野川
高木　洋一
敦司 藤本
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Ａｇｃ株式会社
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Priority to JP2020515473A priority Critical patent/JP7310803B2/ja
Publication of WO2019208546A1 publication Critical patent/WO2019208546A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
    • C07C21/02—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds
    • C07C21/18—Acyclic unsaturated compounds containing halogen atoms containing carbon-to-carbon double bonds containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B61/00—Other general methods

Definitions

  • the present invention relates to a method for efficiently producing a fluorine-containing unsaturated hydrocarbon, specifically, a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin or a chlorofluoroolefin in a liquid phase.
  • fluorine-containing saturated hydrocarbons have been used for cleaning agents, refrigerants, foaming agents, solvents, aerosols and the like. However, it has been pointed out that these compounds may cause global warming. Therefore, fluorine-containing unsaturated hydrocarbons have attracted attention as compounds having a low global warming potential.
  • fluorine-containing saturated hydrocarbons having a structure in which a hydrogen atom and a fluorine atom or a chlorine atom are bonded to two adjacent carbon atoms are removed. Reactions of hydrogen chloride or dehydrofluorination are known.
  • Patent Document 1 discloses a reaction in which XCF 2 CF 2 CHClY is dehydrofluorinated to obtain XCF 2 CF ⁇ CClY (X and Y are fluorine atoms or chlorine atoms), and 1,1 1,2,2,3,3-hexafluoro-3-chloropropane is dehydrochlorinated to give hexafluoropropene.
  • Patent Document 2 describes a method for producing 1-chloro-2,3,3-trifluoropropene by dehydrofluorinating 1-chloro-2,2,3,3-tetrafluoropropane.
  • Patent Document 3 1,1-dichloro-2,2,3,3,3-pentafluoropropane is subjected to dehydrofluorination to produce 1,1-dichloro-2,3,3,3-tetrafluoro.
  • a method for obtaining propene is described.
  • the present invention has been made from the above viewpoint, and in a short reaction time by liquid phase reaction, more efficiently from fluorine-containing saturated hydrocarbon to fluorine-containing unsaturated hydrocarbon, specifically, hydrofluoroolefin, perfluoro
  • the object is to provide a method for producing an olefin, hydrochlorofluoroolefin or chlorofluoroolefin.
  • Fluorine-containing saturated carbonization having a structure having 3 to 7 carbon atoms, wherein one of adjacent two carbon atoms is bonded to a hydrogen atom, and the other carbon atom is bonded to a fluorine atom or a chlorine atom.
  • a method for producing a fluorinated unsaturated hydrocarbon by contacting hydrogen with an alkaline aqueous solution to dehydrochlorinate or dehydrofluorinate, wherein either one of the fluorinated saturated hydrocarbon and the alkaline aqueous solution is an average solution.
  • a method for producing a fluorine-containing unsaturated hydrocarbon wherein a droplet having a droplet diameter of 1500 ⁇ m or less is brought into contact with the droplet.
  • the fluorine-containing saturated hydrocarbon is 1-chloro-2,2,3,3-tetrafluoropropane
  • the fluorine-containing unsaturated hydrocarbon is 1-chloro-2,3,3-trifluoropropene.
  • the fluorine-containing saturated hydrocarbon is 1,1-dichloro-2,2,3,3,3-pentafluoropropane
  • the fluorine-containing unsaturated hydrocarbon is 1,1-dichloro-2,3,
  • the phase transfer catalyst is present in a ratio of 0.001 to 10 parts by mass with respect to 100 parts by mass of the fluorine-containing saturated hydrocarbon.
  • the alkaline aqueous solution is an aqueous solution in which at least one base selected from the group consisting of metal hydroxides, metal oxides and metal carbonates is dissolved in water.
  • Manufacturing method [11] The production method according to any one of [1] to [10], wherein the content of the base in the alkaline aqueous solution is 0.5 to 48% by mass with respect to the total amount of the alkaline aqueous solution.
  • a liquid phase reaction can be carried out more efficiently in a short reaction time, and more efficiently from a fluorine-containing saturated hydrocarbon to a fluorine-containing unsaturated hydrocarbon, specifically, hydrofluoroolefin, perfluoroolefin, hydrochlorofluoroolefin or chloro Fluoroolefins can be produced.
  • a reactor smaller than a gas phase reaction can be employed, which is industrially advantageous.
  • Hydrofluorocarbon is a compound in which a part of hydrogen atoms in a saturated hydrocarbon compound is replaced with a fluorine atom
  • hydrochlorofluorocarbon is a compound in which a part of hydrogen atoms in a saturated hydrocarbon compound is replaced with a fluorine atom and a chlorine atom.
  • a compound having a carbon-carbon double bond and comprising a carbon atom, a fluorine atom and a hydrogen atom is a hydrofluoroolefin (HFO), having a carbon-carbon double bond, a carbon atom, a chlorine atom, a fluorine
  • HFO hydrofluoroolefin
  • HCFO hydrochlorofluoroolefin
  • PFO perfluoroolefin
  • CFO chloro fluoroolefin
  • reaction (1) The reaction represented by the reaction formula (1) is referred to as reaction (1).
  • reaction (2) The same applies to reactions represented by other formulas.
  • compound (A) The compound represented by formula (A).
  • compound (A) The same applies to compounds represented by other formulas.
  • Each of “ ⁇ ” representing a numerical range includes an upper limit value and a lower limit value.
  • pressure “MPa” represents “absolute pressure”
  • MPaG” represents “gauge pressure”.
  • the production method of the present invention has 3 to 7 carbon atoms, and fluorine-containing saturated carbonization having a structure in which a hydrogen atom and a fluorine atom or a chlorine atom are bonded to two adjacent carbon atoms in the molecule.
  • Hydrogen specifically, hydrofluorocarbon (HFC) or hydrochlorofluorocarbon (HCFC) is brought into contact with an alkaline aqueous solution in a liquid phase, and the HFC or HCFC is dehydrochlorinated or dehydrofluorinated to produce a hydrofluoroolefin ( HFO), perfluoroolefin (PFO), hydrochlorofluoroolefin (HCFO), and chlorofluoroolefin (CFO).
  • HFO hydrofluoroolefin
  • PFO perfluoroolefin
  • HCFO hydrochlorofluoroolefin
  • CFO chlorofluoroolefin
  • the HF Or average drop
  • reaction to which the production method of the present invention can be applied is specifically a reaction shown in the following reaction formula (1).
  • the fluorine-containing saturated hydrocarbon of the starting material (raw material) is represented by the formula (A)
  • the fluorine-containing unsaturated hydrocarbon of the target product is represented by the formula (B).
  • Formula (C) is hydrogen chloride or hydrogen fluoride.
  • X 1 and X 2 are a hydrogen atom, and the other is a fluorine atom or a chlorine atom.
  • Y 1 and Y 2 are each independently a hydrogen atom, a fluorine atom or a chlorine atom.
  • R 1 and R 2 are each independently a hydrogen atom, a fluorine atom, a chlorine atom or an aliphatic saturated hydrocarbon group having 1 to 5 carbon atoms (however, part or all of the hydrogen atoms are chlorine atoms or fluorine atoms) And the total number of carbon atoms of R 1 and R 2 is 1-5.
  • One of Y 1 , Y 2 , R 1 and R 2 has a fluorine atom.
  • reaction (1) when compound (A) is brought into contact with an alkaline aqueous solution in the liquid phase, as shown in reaction (1), hydrogen chloride or hydrogen fluoride is eliminated from compound (A) to obtain compound (B).
  • This reaction is carried out in a two-phase state of an organic phase mainly composed of the compound (A) and an aqueous phase mainly composed of an alkaline aqueous solution, and even if mixing is carried out for efficient contact between the two phases by stirring or the like.
  • Increasing speed and improving productivity has not been easy. This is because there is no standard index, and it is not easy to determine the condition setting for bringing the two-phase contact into an optimum state for each apparatus.
  • the present inventors made contact with either one of the compound (A) and the aqueous alkaline solution as droplets having an average droplet diameter of 1500 ⁇ m or less, thereby making it more efficient in a short reaction time. It discovered that a compound (B) can be manufactured and completed this invention.
  • the compound (A) and the alkaline aqueous solution when the compound (A) mainly composed of the organic phase and the alkaline aqueous solution mainly composed of the aqueous phase are brought into contact with each other by stirring due to the difference in surface tension.
  • reaction to which the production method of the present invention can be applied Specific examples of reactions to which the production method of the present invention can be applied will be described below.
  • fluorine-containing unsaturated carbonization represented by the reactions of the following formulas (1-1) to (12-2), (15-1) and (15-2) Examples of hydrogen production are given.
  • Examples of the case of 4 carbon atoms include production examples of fluorine-containing unsaturated hydrocarbons represented by the reactions of the following formulas (13-1) and (13-2).
  • An example of the case of 5 carbon atoms is a production example of a fluorine-containing unsaturated hydrocarbon represented by the reaction of the following formulas (14-1) and (14-2).
  • Formula (1-1) is 3,3-dichloro-1,1,1,2,2-pentafluoropropane (HCFC-225ca) and / or 1,1-dichloro-1,2,3,3,3-
  • a reaction formula for obtaining 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya) from pentafluoropropane (HCFC-225ea) by dehydrofluorination (hereinafter also referred to as deHF). is there.
  • Formula (1-2) is 2,3,3-trichloro-1,1,1,2-tetrafluoropropane (HCFC-224ba) and / or 1,1,1-trichloro-2,3,3,3
  • Formula (2-1) represents 1,1,1,2,2,3,3-heptafluoropropane (HFC-227ca) and / or 1,1,1,2,3,3,3-heptafluoropropane.
  • This is a reaction formula for obtaining hexafluoropropene (PFO-1216) from (HFC-227ea) by deHF.
  • Formula (2-2) is 2-chloro-1,1,1,2,3,3-hexafluoropropane (HCFC-226ba) and / or 1-chloro-1,1,2,3,3,3
  • Formula (3-1) represents 3-chloro-1,1,1,2,2-pentafluoropropane (HCFC-235cb) and / or 3-chloro-1,1,1,2,3-pentafluoropropane
  • deHF from (HCFC-235ea) (Z) -1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (Z)) and / or (E) -1-chloro-2,3 , 3,3-tetrafluoropropene (HCFO-1224yd (E)).
  • Formula (3-2) represents 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb) and / or 3,3-dichloro-1,1,1,2-tetrafluoropropane This is a reaction formula for obtaining HCFO-1224yd (Z) and / or HCFO-1224yd (E) from (HCFC-234ea) by removing HCl.
  • Formula (4-1) is a compound represented by 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and / or 2-chloro-1,1,1,3-tetrafluoropropane (HCFC-244db).
  • HCFC-244bb 2-chloro-1,1,1,3-tetrafluoropropane
  • HCFC-244db 2-chloro-3,3,3-trifluoropropene
  • Formula (4-2) is a compound represented by 2,2-dichloro-1,1,1-trifluoropropane (HCFC-243xb) and / or 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db). Is a reaction formula for obtaining HCFO-1233xf from HCl by dehydrochlorination.
  • Formula (5-1) is a compound represented by the following formula: 3-chloro-1,1,2,2-tetrafluoropropane (HCFC-244ca) and / or 1-chloro-1,2,3,3-tetrafluoropropane (HCFC-244ea) ) To (Z) -1-chloro-2,3,3-trifluoropropene (HCFO-1233yd (Z)) and / or (E) -1-chloro-2,3,3-trifluoropropene This is a reaction formula for obtaining (HCFO-1233yd (E)).
  • Formula (5-2) is a compound represented by 2,3-dichloro-1,1,2-trifluoropropane (HCFC-243ba) and / or 1,1-dichloro-2,3,3-trifluoropropane (HCFC-243eb).
  • Formula (6-1) is a compound represented by the following formula: 3-chloro-1,1,1,2-tetrafluoropropane (HCFC-244eb) and / or 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa).
  • HCFC-244eb 3-chloro-1,1,1,2-tetrafluoropropane
  • HCFC-244fa 3-chloro-1,1,1,3-tetrafluoropropane
  • Formula (6-2) is a compound represented by 2,3-dichloro-1,1,1-trifluoropropane (HCFC-243db) and / or 3,3-dichloro-1,1,1-trifluoropropane (HCFC-243fa).
  • Formula (7-1) is obtained by removing HF from 1,1,1,2,2-pentafluoropropane (HFC-245cb) and / or 1,1,1,2,3-pentafluoropropane (HFC-245eb). Is a reaction formula for obtaining 2,3,3,3-tetrafluoropropene (HFO-1234yf).
  • Formula (7-2) is a compound represented by 2-chloro-1,1,1,2-tetrafluoropropane (HCFC-244bb) and / or 3-chloro-1,1,1,2-tetrafluoropropane (HCFC-244eb). ) To obtain HFO-1234yf by deHCl.
  • Formula (8-1) is obtained by removing HF from 1,1,1,2,3-pentafluoropropane (HFC-245eb) and / or 1,1,1,3,3-pentafluoropropane (HFC-245fa).
  • Is a reaction formula to obtain Formula (8-2) is a compound represented by 2-chloro-1,1,1,3-tetrafluoropropane (HCFC-244db) and / or 3-chloro-1,1,1,3-tetrafluoropropane (HCFC-244fa).
  • Formula (9-1) represents 2,3-dichloro-1,1,1,2-tetrafluoropropane (HCFC-234bb) and / or 2,3-dichloro-1,1,1,3-tetrafluoropropane (HC) -234da) to (Z) -1,2-dichloro-3,3,3-trifluoropropene (HCFO-1223xd (Z)) and / or (E) -1,2-dichloro-3 , 3,3-trifluoropropene (HCFO-1223xd (E)).
  • Formula (9-2) represents 2,2,3-trichloro-1,1,1-trifluoropropane (HCFC-233ab) and / or 2,3,3-trichloro-1,1,1-trifluoropropane This is a reaction formula for obtaining HCFO-1223xd (Z) and / or HCFO-1223xd (E) from (HCFC-233da) by de-HCl.
  • Formula (10-1) is represented by 1,1,1,2,2,3-hexafluoropropane (HFC-236cb) and / or 1,1,1,2,3,3-hexafluoropropane (HFC-236eb).
  • HFC-236cb 1,1,1,2,3,3-hexafluoropropane
  • HFC-236eb 1,1,1,2,3,3-hexafluoropropane
  • Formula (10-2) is 2-chloro-1,1,1,2,3-pentafluoropropane (HCFC-235bb) and / or 3-chloro-1,1,1,2,3-pentafluoropropane This is a reaction formula for obtaining HFO-1225ye (Z) and / or HFO-1225ye (E) by removing HCl from (HCFC-235ea).
  • Formula (11-1) can be obtained by removing HF from 1,1,1,2-tetrafluoropropane (HFC-254eb) and / or 1,1,1,3-tetrafluoropropane (HFC-254fb) to form 3,3 , 3-trifluoropropene (HFO-1243zf) is obtained.
  • Formula (11-2) is obtained by removing HCl from 2-chloro-1,1,1-trifluoropropane (HCFC-253db) and / or 3-chloro-1,1,1-trifluoropropane (HCFC-244eb). Is a reaction formula for obtaining HFO-1243zf.
  • Formula (12-1) is obtained by removing 3,1,3-difluoropropene (HFC-263eb) and / or 1,1,3-trifluoropropane (HFC-263fa) by deHF. This is a reaction formula to obtain HFO-1252zf).
  • Formula (12-2) yields HFO-1252zf from 2-chloro-1,1-difluoropropane (HCFC-262db) and / or 3-chloro-1,1-difluoropropane (HCFC-262fa) by de-HCl It is a reaction formula.
  • Formula (13-1) is obtained by removing HF from 1,1,1,2,4,4-heptafluorobutane (HFC-347mef) and (Z) -1,1,1,4,4,4- Reaction to obtain hexafluoro-2-butene (HFO-1336mzz (Z)) and / or (E) -1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz (E)) It is a formula.
  • Formula (13-2) is obtained by removing HFO-1336mzz (Z) or HFO-1336mzz (E) from 2-chloro-1,1,1,4,4,4-hexafluorobutane (HCFC-346mdf) by removing HCl. It is the reaction formula to be obtained.
  • Formula (14-1) is a compound represented by the following formula: 5-chloro-1,1,2,2,3,3,4,4-octafluoropentane (HCFC-448occc) and / or 5-chloro-1,1,2,2 (Z) -1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HC), 3,4,5-octafluoropentane (HCFC-448 pcce) by deHF Reaction formula to obtain HCFO-1437 dycc (Z)) and / or (E) -1-chloro-2,3,3,4,4,5,5-heptafluoro-1-pentene (HCFO-1437 dycc (E)) It is.
  • Formula (14-2) is a compound represented by 4,5-dichloro-1,1,2,2,3,3,4-heptafluoropentane (HCFC-447 obscc) and / or 5,5-dichloro-1,1,2, , 2,3,3,4-heptafluoropentane (HCFC-447necc) to remove HCFO-1437 dycc (Z) and / or HCFO-1437 dycc (E) by removing HCl.
  • HCFC-447 obscc 4,5-dichloro-1,1,2,2,3,3,4-heptafluoropentane
  • HCFC-447necc 5,5-dichloro-1,1,2, , 2,3,3,4-heptafluoropentane
  • Formula (15-1) is a compound represented by the following formula: 3-chloro-1,1,1,2,2,3-hexafluoropropane (HCFC-226ca) and / or 1-chloro-1,1,2,3,3,3 By deHF from hexafluoropropane (HCFC-226ea) (Z) -1-chloro-1,2,3,3,3-pentafluoropropene (CFO-1215yb (Z)) and / or (E) -1 This is a reaction formula for obtaining -chloro-1,2,3,3,3-pentafluoropropene (CFO-1215yb (E)).
  • Formula (15-2) is a compound represented by 2,3-dichloro-1,1,1,2,3-pentafluoropropane (HCFC-225ba) and / or 1,1-dichloro-1,2,3,3,3.
  • reaction rate can be improved and the reaction can be efficiently carried out.
  • 225 ca is removed by HF to 1214 ya.
  • reaction (5-1) 1233yd (Z) and / or 1233yd (E) is obtained from 244ca by deHF, and 1233xf is obtained from 243db by deHCl in reaction (4-2).
  • reaction (6-2) 1233zd (Z) is obtained by removing HCl from 243fa
  • reaction (9-2) 1223xd (Z) and / or 1223xd (E) is obtained by removing HCl from 233da
  • the reaction to obtain is mentioned.
  • reaction (1-1) a reaction to obtain 1214ya from 225ca by deHF
  • reaction (5-1) a reaction to obtain 1233yd (Z) and / or 1233yd (E) from 244ca by deHF
  • reaction (9-2) is more preferably a reaction in which 1223xd (Z) and / or 1223xd (E) is obtained from 233da by deHCl.
  • the reaction since the compound produced by the dehydrohalogenation reaction does not volatilize at room temperature, the produced compound becomes bubbles and the reaction is efficiently performed without inhibiting the contact between the alkaline aqueous solution and the raw material. Can be implemented. Furthermore, from the viewpoint that the reaction can be carried out efficiently, among the reaction (1-1), the reaction to obtain 1214ya from 225ca by deHF, and among the reaction (5-1), 1233yd (Z) and from 244ca by deHF Or the reaction which obtains 1233yd (E) is more preferable.
  • the compound (A) is in a liquid phase as an organic phase and is in physical contact with an alkaline aqueous solution, more specifically, by contacting with a base in the alkaline aqueous solution.
  • DeHF or deHCl reaction occurs to produce compound (B).
  • either the compound (A) or the alkaline aqueous solution in the form of droplets, and the average droplet diameter of the droplets is 1500 ⁇ m or less.
  • the compound (A) may be a droplet, and an alkaline aqueous solution may be a droplet. Any one of them is appropriately selected depending on the type and amount of the compound (A) and the aqueous alkali solution to form droplets. From the viewpoint of increasing the reaction rate, the compound (A) is preferably brought into contact with an alkaline aqueous solution as droplets.
  • the average droplet diameter of the droplet is preferably 800 ⁇ m or less, more preferably 600 ⁇ m or less, and even more preferably 400 ⁇ m or less.
  • the average droplet diameter of the droplets is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, preferably 30 ⁇ m or more, and most preferably 50 ⁇ m or more.
  • the average droplet diameter is less than 1 ⁇ m, the entire reaction solution is emulsified, and it may be difficult to separate the target product compound (B) from the reaction solution.
  • Examples of the method of setting the average droplet diameter of either the compound (A) or the alkaline aqueous solution to 1500 ⁇ m or less include a method using a conventionally known apparatus.
  • Examples of such an apparatus include a stirring blade, a line mixer, a homogenizer, an ultrasonic generator, a microbubble generator, and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type as needed.
  • the droplets having an average droplet diameter of the size specified above are batch-type, semi-continuous type Or it is preferable to make it produce
  • the stirring blade include a 4-paddle blade, an anchor blade, a gate blade, a 3-propeller, a ribbon blade, and a 6-turbine blade.
  • the average droplet diameter d p (m) of the compound (A) or the aqueous alkali solution formed in the stirring tank is represented by the following formula (16).
  • d p / d i C * We ⁇ 0.6
  • d i is the inner diameter (m) of the stirring blade
  • We is the Weber number
  • C is a constant.
  • We ⁇ * N 2 * d i 3 / ⁇ .
  • ⁇ is the density of the droplet component (kg / m 3 )
  • N is the rotational speed (rps) of stirring
  • ⁇ is the difference in surface tension (Nm ⁇ 1 ) between the compound (A) and the alkaline aqueous solution. .
  • C is for correcting the influence on the average droplet diameter, and can be experimentally obtained from the correlation between the number of rotations of stirring and the droplet diameter in the stirring tank. That is, when the relationship between the number of rotations of stirring and the droplet diameter is plotted, it is almost linear, and the slope is C. Further, for example, the value of C obtained from the experimental results described in Non-Patent Document 1 (Calderbank, PH, Trans. Inst. Chem. Engrs., 36, 443) may be referred to. C is usually 0.052 to 0.17.
  • C is usually 0.052 to 0.17, preferably 0.055 to 0.070.
  • the compound (A) and an aqueous alkali solution are usually introduced into a reactor, and droplets are generated using the apparatus for generating the droplets.
  • the material of the reactor is not particularly limited as long as it is inert to the compound (A), a phase transfer catalyst described later, an alkaline aqueous solution, a reaction solution component containing a reaction product, and the like, and is a corrosion-resistant material.
  • glass, iron, nickel, an alloy such as stainless steel mainly containing iron, or the like can be given.
  • the reaction in the present invention may be performed by a batch method, a semi-continuous method, or a continuous flow method. Compared to the case where the average droplet diameter is not adjusted within the scope of the present invention, the reaction time can be shortened in any manner.
  • either the compound (A) or the alkaline aqueous solution is present as droplets at any location in the reactor, and the average droplet diameter of the droplets May be 1500 ⁇ m or less.
  • the compound (A) or the aqueous alkaline solution is present as droplets, and the average droplet diameter of the droplets is 1500 ⁇ m or less.
  • the droplet diameter is either a compound (A) or an alkaline aqueous solution at any time during the reaction, and the average droplet diameter of the droplet is 1500 ⁇ m or less. If it is.
  • the compound (A) or the alkaline aqueous solution is present as droplets, and the average droplet diameter of the droplets is 1500 ⁇ m or less.
  • the ratio of the compound (A) to be introduced into the reactor and the aqueous alkali solution is not particularly limited as long as either of them is a ratio within which the droplets are within the above regulations.
  • the alkaline aqueous solution is preferably 10 to 400% by volume, more preferably 50 to 300% by volume with respect to 100% by volume of the compound (A).
  • the volume ratio of the compound (A) and the aqueous alkaline solution is the compound (A) and the alkali to be combined in consideration of the preferable use amount of the base with respect to the compound (A), the preferable content of the base in the aqueous alkaline solution, etc. It adjusts suitably according to the kind of aqueous solution.
  • the alkaline aqueous solution used in the production method of the present invention refers to an aqueous solution in which a base is dissolved in water.
  • the base is not particularly limited as long as the above reaction (1) can be performed.
  • the base preferably contains at least one selected from the group consisting of metal hydroxides, metal oxides and metal carbonates.
  • examples include alkaline earth metal hydroxides and alkali metal hydroxides.
  • examples of the alkaline earth metal hydroxide include magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide.
  • examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and potassium hydroxide.
  • examples of the metal constituting the metal oxide include an alkali metal element, an alkaline earth metal element, a transition metal element, a Group 12 metal element, and a Group 13 metal element.
  • alkali metal elements, alkaline earth metal elements, Group 6 metal elements, Group 8 metal elements, Group 10 metal elements, Group 12 metal elements, or Group 13 metal elements are preferable, and sodium, calcium, chromium More preferred are iron, zinc, or aluminum.
  • the metal oxide may be an oxide containing one kind of metal or a complex oxide of two or more kinds of metals.
  • sodium oxide, calcium oxide, chromium oxide (chromia), aluminum oxide (alumina), zinc oxide and the like are preferable from the viewpoint of reaction time and reaction yield, and alumina or chromia is more preferable.
  • examples include alkaline earth metal carbonates and alkali metal carbonates.
  • alkaline earth metal carbonate include carbonates of metals such as beryllium, magnesium, calcium, strontium, barium, and radium.
  • alkali metal carbonate include metal carbonates such as lithium, sodium, potassium, rubidium, cesium, and francium.
  • the base used in the production method of the present invention is preferably a metal hydroxide from the viewpoint of reaction time and reaction yield, and particularly preferably at least one selected from the group consisting of potassium hydroxide and sodium hydroxide.
  • a metal hydroxide may be used individually by 1 type and may use 2 or more types together.
  • the content of the base in the alkaline aqueous solution is preferably such that the ratio (unit%) of the mass of the base to the total amount (mass) of the alkaline aqueous solution is 0.5 to 48% by mass from the viewpoint of reaction rate, and 20 to 45% by mass. % Is more preferable, and 30 to 40% by mass is further preferable. If the amount of base is less than the above range, a sufficient reaction rate may not be obtained. On the other hand, when the amount of the base exceeds the above range, the amount of by-products generated increases, and the selectivity for the target substance (compound (B)) may decrease.
  • the amount of base used in the production method of the present invention depends on the type of reaction (1).
  • the amount of base used is preferably 0.5 to 10.0 moles with respect to 1 mole of 244ca from the viewpoint of the reaction yield and the selectivity of 1233yd. 0.5 to 5.0 mol is more preferable, and 0.8 to 3.0 mol is more preferable.
  • the amount of the base used is preferably 0.5 to 2.0 mol with respect to 1 mol of 225ca from the viewpoint of the reaction yield and the selectivity of 1214ya.
  • 0.5 to 1.8 mol is more preferable, and 1.0 to 1.5 mol is more preferable.
  • reaction conditions other than those described above in the reaction (1) for example, temperature, pressure, etc., can be generally the same as the reaction conditions when the alkaline aqueous solution and the compound (A) are contacted in the liquid phase to cause deHF or deHCl reaction. .
  • the contact temperature between 244ca and the base is preferably 5 to 90 ° C, more preferably 10 to 85 ° C, from the viewpoint of the reaction activity and the selectivity of 1233yd. 15 to 80 ° C. is more preferable, and 30 to 80 ° C. is particularly preferable.
  • the reaction temperature does not reach the above range, the reaction rate and the reaction yield may be reduced.
  • separation from 1233yd may be difficult.
  • 1233yd may further increase the amount of 1-chloro-3,3-difluoropropyne produced by dehydrofluorination and the selectivity of 1233yd may decrease. There is sex.
  • reaction to obtain 1214ya from 225ca by deHF from the viewpoint of reaction activity and target product selectivity, 0 to 90 ° C is preferable, 5 to 80 ° C is more preferable, and 10 to 70 ° C is more preferable. Most preferred is 15-60 ° C.
  • a compound (A) may be used with the by-product and unreacted raw material byproduced at the time of manufacture of a compound (A).
  • it can use for the manufacturing method of this invention as a composition of a compound (A) whose purity is 99.5 mass% or more.
  • 225ca may be used as an isomer mixture of dichloropentafluoropropane (HCFC-225) containing 225ca, in which case the total amount of HCFC-225 The proportion of 225ca may be 10-99.5 mol%.
  • the reaction temperature is preferably 0 to 25 ° C. from the viewpoint of suppressing the formation of by-products.
  • a phase transfer catalyst is preferably present.
  • phase transfer catalyst examples include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, sulfonium salts, crown ethers, etc., and are quaternary from the viewpoint of industrial availability, price, and ease of handling. Ammonium salts are preferred.
  • TBAC tetra-n-butylammonium chloride
  • TBAB tetra-n-butylammonium bromide
  • TOMAC methyltri-n-octylammonium chloride
  • TBAC tetra-n-butylammonium chloride
  • TBAC tetra-n-butylammonium bromide
  • TOMAC methyltri-n-octylammonium chloride
  • TBAC tetra-n-butylammonium chloride
  • TBAB tetra-n-butylammonium bromide
  • TBAC tetra-n-butylammonium bromide
  • TBAC tetra-n-butylammonium chloride
  • TBAC tetra-n-butylammonium chloride
  • TOMAC methyltri-n-octylammonium chloride
  • the amount of the phase transfer catalyst is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass with respect to 100 parts by mass of the compound (A). . If the amount of the phase transfer catalyst is too small, a sufficient reaction rate may not be obtained, and even if it is used in a large amount, a reaction promoting effect according to the amount used cannot be obtained, which is disadvantageous in terms of cost.
  • the phase transfer catalyst exists both in the organic phase and in the alkaline aqueous solution. Even when a phase transfer catalyst is present, the reaction liquid is composed of an organic phase mainly composed of the compound (A) and an aqueous phase composed of an alkaline aqueous solution, and any of the phases has a liquid droplet diameter as defined above. By using droplets, the reaction time is shortened and productivity is improved.
  • the reaction rate can be improved by setting the droplet diameter of the compound (A) or the aqueous alkali solution within the above specified range, the amount of the phase transfer catalyst used can be reduced accordingly. Even in this respect, the manufacturing cost can be reduced.
  • the amount of the phase transfer catalyst can be sufficiently reacted even with 0.001 to 1 part by mass with respect to 100 parts by mass of the compound (A).
  • the reaction solution is left to separate into an organic phase and an aqueous phase.
  • an unreacted compound (A), a by-product and the like may be contained in addition to the target product compound (B).
  • a separation and purification method such as general distillation.
  • the compound (A) when the unreacted compound (A) remains in the reaction solution, the compound (A) can be concentrated by distillation and recycled as the raw material of the present invention.
  • the aqueous phase separated from the organic phase can be reused by taking out only this amount and adding a base again so as to obtain an appropriate concentration.
  • the purified compound (B) containing the compound (B) with high purity can be obtained by separating and purifying the compound (B) obtained by the production method of the present invention as described above.
  • the purified compound (B) thus obtained contains an acid content such as HF or HCl, or an impurity such as water or oxygen, the equipment corrodes during its use, and the stability of the compound (B) decreases. There is a risk of. Therefore, it is preferable to remove these impurities by a conventionally known method to such an extent that there is no problem with corrosion and stability.
  • 244ca was produced by the following method and used in Examples 1 to 7 and Comparative Example 1.
  • the following method is a method of obtaining 244ca by chlorinating 2,2,3,3-tetrafluoropropanol (TFPO) with thionyl chloride as shown in the following formula (2).
  • Example 1 In a 200 mL autoclave (reactor, 200 ml AC) made of SUS304 equipped with four paddle blades, a stirrer, and a pressure meter, 171 g of 34.0 mass% potassium hydroxide (KOH) aqueous solution was placed and heated to 50 ° C. Further, 0.78 g of tetra-n-butylammonium bromide (TBAB) was dissolved in 76.4 g of 244ca, filled into a cylinder, and heated to 50 ° C. When the internal temperature of the reactor reached 50 ° C., the 244ca solution in the cylinder was charged into the reactor. Thereafter, stirring was continued for 45 hours until the conversion of 244ca reached 99.8% or more, and the organic layer and the aqueous layer were recovered.
  • KOH 34.0 mass% potassium hydroxide
  • TBAB tetra-n-butylammonium bromide
  • Table 1 shows the dimensions of the reactor, reaction conditions, and results.
  • the conversion rate is the ratio (unit:%) of the molar amount of the raw material (244ca) consumed in the reaction to the molar amount of the raw material (244ca) used in the reaction. Show.
  • the reaction time in Table 1 is the time required from the start of the reaction until the conversion rate of 244ca reaches 99.8% or more.
  • Example 2 A glass 500 ml separable flask (reactor) equipped with a gate blade, a stirrer, and a Dimroth condenser was charged with 333 g of 34 mass% KOH aqueous solution, 156 g of 244ca, and 1.59 g of TBAB. The reactor was heated to 50 ° C. and stirring was continued. The reaction was terminated after 30 hours from the start of stirring, and collection and analysis were conducted in the same manner as in Example 1. As a result, it was confirmed that 1233yd, which is the target substance, was produced in the organic phase. Table 1 shows the dimensions of the reactor, reaction conditions, and results.
  • Example 3 The reaction was carried out in the same procedure as in Example 2 except that the reactor was changed to a glass 500 ml separable flask equipped with three propellers, a stirrer and a Dimroth condenser, and the reaction conditions were changed to the conditions shown in Table 1. went. When recovery and analysis were performed in the same manner as in Example 1, it was confirmed that 1233yd, which is the target substance, was produced in the organic phase. Table 1 shows the dimensions of the reactor, reaction conditions, and results.
  • Examples 4 to 6 The reaction was performed in the same reactor and procedure as in Example 3 except that the reaction conditions were changed to those shown in Table 1. When recovery and analysis were performed in the same manner as in Example 1, it was confirmed that 1233yd, which is the target substance, was produced in the organic phase. Table 1 shows the dimensions of the reactor, reaction conditions, and results.
  • Example 7 Into a 2500 mL autoclave (reactor, 2500 ml AC) manufactured by HC276C equipped with four paddle blades, a stirrer, and a pressure meter, 988 g of 34 mass% potassium hydroxide (KOH) aqueous solution was placed, and the reactor was heated to 70 ° C. Further, 3.87 g of tetra-n-butylammonium chloride (TBAC) was dissolved in 450 g of 244ca, filled into a cylinder, and heated to 70 ° C. When the reactor internal temperature reached 70 ° C., the 244ca solution in the cylinder was charged into the reactor.
  • KOH potassium hydroxide
  • TBAC tetra-n-butylammonium chloride
  • Example 8 The raw material was changed to 225ca (Asahi Glass Co., Ltd., purity 100%, the same applies to the following), the alkaline solution was changed to a 40 mass% potassium hydroxide (KOH) aqueous solution, and the reaction conditions were changed to the conditions shown in Table 2. The reaction was carried out in the same reactor and procedure as in Example 1. When recovery and analysis were performed in the same manner as in Example 1, it was confirmed that 1214ya which is the target substance was produced in the organic phase. Table 2 shows reactor dimensions, reaction conditions, and results.
  • KOH potassium hydroxide
  • the conversion rate indicates the ratio (unit:%) of the molar amount of the raw material (225ca) consumed in the reaction to the molar amount of the raw material (225ca) used in the reaction.
  • the reaction time in Table 2 is the time required from the start of the reaction until the conversion of 225ca reaches 99.8% or more.
  • Example 9 The reaction was carried out in the same reactor and procedure as in Example 2 except that the raw material was changed to 225ca, the alkaline solution was changed to a 40 mass% potassium hydroxide (KOH) aqueous solution, and the reaction conditions were changed to the conditions shown in Table 2. It was. When recovery and analysis were performed in the same manner as in Example 1, it was confirmed that 1214ya which is the target substance was produced in the organic phase. Table 2 shows reactor dimensions, reaction conditions, and results.
  • KOH potassium hydroxide
  • Example 10 and 11 The reaction was carried out in the same reactor and procedure as in Example 3, except that the raw material was changed to 225ca, the alkaline solution was changed to a 40 mass% potassium hydroxide (KOH) aqueous solution, and the reaction conditions were changed to the conditions shown in Table 2. It was. When recovery and analysis were performed in the same manner as in Example 1, it was confirmed that 1214ya which is the target substance was produced in the organic phase. Table 2 shows reactor dimensions, reaction conditions, and results.
  • KOH potassium hydroxide
  • Example 2 The reaction was carried out in the same reactor and procedure as in Example 3, except that the raw material was changed to 225ca, the alkaline solution was changed to a 40 mass% potassium hydroxide (KOH) aqueous solution, and the reaction conditions were changed to the conditions shown in Table 2. It was. When recovery and analysis were performed in the same manner as in Example 1, it was confirmed that 1214ya which is the target substance was produced in the organic phase. Table 2 shows reactor dimensions, reaction conditions, and results.
  • KOH potassium hydroxide

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Abstract

La présente invention concerne un procédé de production d'un hydrocarbure insaturé contenant du fluor, plus particulièrement une hydrofluorooléfine, une perfluorooléfine, une hydrochlorofluorooléfine ou une chlorofluorooléfine à partir d'un hydrocarbure saturé contenant du fluor de manière plus efficace au moyen d'une réaction en phase liquide, en un temps de réaction plus court. L'invention concerne un procédé de production d'un hydrocarbure insaturé contenant du fluor par déshydrochloration ou par élimination de fluorure d'hydrogène consistant à mettre en contact un hydrocarbure saturé contenant du fluor ayant de 3 à 7 atomes de carbone et ayant une structure dont l'un des deux atomes de carbone adjacents est lié avec un atome d'hydrogène et l'autre est lié avec un atome de fluor ou un atome de chlore, avec une solution alcaline aqueuse. Ce procédé de production d'un hydrocarbure insaturé contenant du fluor est caractérisé en ce que l'un ou l'autre de l'hydrocarbure saturé contenant du fluor et de la solution alcaline aqueuse est mis en contact l'un avec l'autre sous forme de gouttelettes ayant un diamètre moyen de gouttelette de 1500 µm ou moins.
PCT/JP2019/017160 2018-04-23 2019-04-23 Procédé de production d'un hydrocarbure insaturé contenant du fluor WO2019208546A1 (fr)

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JPH07268090A (ja) * 1994-03-29 1995-10-17 Idemitsu Petrochem Co Ltd ポリカーボネートの製造方法
JP2004018624A (ja) * 2002-06-14 2004-01-22 Teijin Chem Ltd 芳香族ポリカーボネート樹脂の製造方法およびその製造装置
WO2010074254A1 (fr) * 2008-12-25 2010-07-01 旭硝子株式会社 Procédés de préparation de 1,1-dichloro-2,3,3,3-tétrafluoropropène et de 2,3,3,3-tétrafluoropropène
WO2011162336A1 (fr) * 2010-06-23 2011-12-29 旭硝子株式会社 Procédé de fabrication de 1,1-dichloro-2,3,3,3-tétra-fluoropropène et de 2,3,3,3-tétrafluoropropène
JP2013519631A (ja) * 2010-02-19 2013-05-30 ダイキン工業株式会社 ２−クロロ−３，３，３−トリフルオロプロペンの製造方法
JP2016079101A (ja) * 2014-10-10 2016-05-16 旭硝子株式会社 １，１−ジクロロ−３，３，３−トリフルオロプロペンの製造方法

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JPH08169850A (ja) * 1994-12-16 1996-07-02 Daikin Ind Ltd １，１，１，２，３，３−ヘキサフルオロプロパンの製造方法
JP3778298B2 (ja) * 1995-01-13 2006-05-24 ダイキン工業株式会社 ヘキサ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
JPH07268090A (ja) * 1994-03-29 1995-10-17 Idemitsu Petrochem Co Ltd ポリカーボネートの製造方法
JP2004018624A (ja) * 2002-06-14 2004-01-22 Teijin Chem Ltd 芳香族ポリカーボネート樹脂の製造方法およびその製造装置
WO2010074254A1 (fr) * 2008-12-25 2010-07-01 旭硝子株式会社 Procédés de préparation de 1,1-dichloro-2,3,3,3-tétrafluoropropène et de 2,3,3,3-tétrafluoropropène
JP2013519631A (ja) * 2010-02-19 2013-05-30 ダイキン工業株式会社 ２−クロロ−３，３，３−トリフルオロプロペンの製造方法
WO2011162336A1 (fr) * 2010-06-23 2011-12-29 旭硝子株式会社 Procédé de fabrication de 1,1-dichloro-2,3,3,3-tétra-fluoropropène et de 2,3,3,3-tétrafluoropropène
JP2016079101A (ja) * 2014-10-10 2016-05-16 旭硝子株式会社 １，１−ジクロロ−３，３，３−トリフルオロプロペンの製造方法

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