WO2019208546A1 - Method for producing fluorine-containing unsaturated hydrocarbon - Google Patents

Abstract

The present invention provides a method for producing a fluorine-containing unsaturated hydrocarbon, specifically a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin or a chlorofluoroolefin from a fluorine-containing saturated hydrocarbon more efficiently by means of a liquid phase reaction in a shorter reaction time. A method for producing a fluorine-containing unsaturated hydrocarbon through dehydrochlorination or hydrogen fluoride elimination by bringing a fluorine-containing saturated hydrocarbon, which has 3-7 carbon atoms and has a structure wherein one of two adjacent carbon atoms is bonded with a hydrogen atom and the other is bonded with a fluorine atom or a chlorine atom, into contact with an aqueous alkaline solution. This method for producing a fluorine-containing unsaturated hydrocarbon is characterized in that either one of the fluorine-containing saturated hydrocarbon and the aqueous alkaline solution is brought into contact with the other in the form of droplets having an average droplet diameter of 1,500 μm or less.

Description

Method for producing fluorine-containing unsaturated hydrocarbon

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.

In recent years, 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.

As one of the methods for producing fluorine-containing unsaturated hydrocarbons, 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.

For example, 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. In 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.

In any of these Patent Documents 1 to 3, an example is described in which the dehydrochlorination or dehydrofluorination reaction of a fluorine-containing saturated hydrocarbon is performed using an aqueous alkali solution in a liquid phase reaction. In these reactions, the reaction time is long. Therefore, although improvements such as the use of a phase transfer catalyst have been made, a method capable of producing more efficiently has been demanded.

Japanese Patent No. 3778298 International Publication No. 2017/018412 International Publication No. 2010/074254

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.

The present invention achieves the above object and has the following aspects.
[1] 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 μm or less is brought into contact with the droplet.

[2] The method according to [1], wherein the fluorine-containing saturated hydrocarbon has an average droplet diameter of 800 μm or less and is brought into contact with an alkaline aqueous solution.
[3] The method according to [1] or [2], wherein the droplets are generated using at least one device selected from a stirring blade, a line mixer, a homogenizer, an ultrasonic generator, and a microbubble generator.
[4] The method according to any one of [1] to [3], wherein the droplets are generated by stirring with a stirring blade.
[5] The method according to any one of [1] to [4], wherein an average droplet diameter of the droplets is 1 μm or more and 400 μm or less.
[6] The fluorine-containing saturated hydrocarbon is 1-chloro-2,2,3,3-tetrafluoropropane, and the fluorine-containing unsaturated hydrocarbon is 1-chloro-2,3,3-trifluoropropene. A production method according to any one of [1] to [5].

[7] The fluorine-containing saturated hydrocarbon is 1,1-dichloro-2,2,3,3,3-pentafluoropropane, and the fluorine-containing unsaturated hydrocarbon is 1,1-dichloro-2,3, The production method of any one of [1] to [5], which is 3,3-tetrafluoropropene.
[8] The production method of any one of [1] to [7], wherein the fluorine-containing saturated hydrocarbon is brought into contact with an alkaline aqueous solution in the presence of a phase transfer catalyst.
[9] The production method of [8], wherein 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.
[10] Any of [1] to [9], wherein 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.

According to the present invention, 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.
In addition, since the production method of the present invention is carried out by a liquid phase reaction, a reactor smaller than a gas phase reaction can be employed, which is industrially advantageous.

The meaning of terms in this specification and the way of description are as follows.
As for the halogenated hydrocarbon, the abbreviation of the compound is described in parentheses after the compound name, but the abbreviation is used instead of the compound name as necessary. In addition, as abbreviations, only numbers after the hyphen (-) and lower-case alphabetic characters (for example, "1224yd" in "HCFO-1224yd") may be used. Furthermore, (E) attached to the names of compounds having geometric isomers and their abbreviations indicate E form (trans form), and (Z) indicates Z form (cis form). In the names and abbreviations of the compounds, when the E-form and Z-form are not specified, the names and abbreviations are generic names including E-form, Z-form, and a mixture of E-form and Z-form.

Hydrofluorocarbon (HFC) is a compound in which a part of hydrogen atoms in a saturated hydrocarbon compound is replaced with a fluorine atom, and hydrochlorofluorocarbon (HCFC) 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 A compound composed of atoms and hydrogen atoms is called hydrochlorofluoroolefin (HCFO), a compound having a carbon-carbon double bond and composed of carbon atoms and fluorine atoms is called perfluoroolefin (PFO), carbon -Having a carbon double bond, carbon atom, chlorine atom or fluorine atom Configured compound of chloro fluoroolefin (CFO).

The reaction represented by the reaction formula (1) is referred to as reaction (1). The same applies to reactions represented by other formulas. The compound represented by formula (A) is referred to as 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.
Regarding “pressure”, “MPa” represents “absolute pressure”, and “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). In the reaction of hydrogen chloride or dehydrofluorination, the HF Or average droplet size one of HCFC and alkaline aqueous solution and wherein the contacting in the following droplet 1500 .mu.m.

(Reaction to which the production method of the present invention can be applied)
The reaction to which the production method of the present invention is applied is specifically a reaction shown in the following reaction formula (1). In the formula (1), the fluorine-containing saturated hydrocarbon of the starting material (raw material) is represented by the formula (A), and the fluorine-containing unsaturated hydrocarbon of the target product is represented by the formula (B). Formula (C) is hydrogen chloride or hydrogen fluoride.

However, the symbols in formula (1) are as follows.
One of X ¹ and X ² is 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.

Conventionally, 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). Are known. 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.

In the above reaction (1), 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 μm 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. In the present 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. By using the phenomenon that any one of the droplets becomes a droplet and adjusting the factor of the average droplet diameter of the droplet, the reaction time of the reaction (1) can be shortened regardless of the type and scale of the apparatus, Compound (B) can be produced with high productivity.

(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. As an example in the case of 3 carbon atoms, 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 A reaction formula for obtaining CFO-1214ya by dehydrochlorinating (hereinafter also referred to as deHCl) of tetrafluoropropane (HCFC-224eb).

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 A reaction formula for obtaining PFO-1216 from hexafluoropropane (HCFC-226ea) by deHCl.

Formula (3-1) represents 3-chloro-1,1,1,2,2-pentafluoropropane (HCFC-235cb) and / or 3-chloro-1,1,1,2,3-pentafluoropropane By 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). ) To give 2-chloro-3,3,3-trifluoropropene (HCFO-1233xf) by deHF. 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). HCHC-1233yd (Z) and / or HCFO-1233yd (E) by dehydrochlorination from HCl.

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). ) To (Z) -1-chloro-3,3,3-trifluoropropene (HCFO-1233zd (Z)) and / or (E) -1-chloro-3,3,3-trifluoropropene This is a reaction formula to obtain (HCFO-1233zd (E)). 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). HCHC-1233zd (Z) and / or HCFO-1233zd (E) by dehydrochlorination from HCl.

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). (Z) -1,3,3,3-tetrafluoropropene (HFO-1234ze (Z)) and / or (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)) 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). ) To obtain HFO-1234ze (Z) and / or HFO-1234ze (E) by deHCl.

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). ) To (Z) -1,2,3,3,3-pentafluoropropene (HFO-1225ye (Z)) and / or (E) -1,2,3,3,3-pentafluoropropene This is a reaction formula to obtain (HFO-1225ye (E)). 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 1,1,1,2,4,4,4-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.

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. A reaction formula for obtaining CFO-1215yb (Z) and / or CFO-1215yb (E) from pentafluoropropane (HCFC-225eb) by deHCl.

In each of the above reactions, particularly as a reaction in which the production method of the present invention is suitably used, the reaction rate can be improved and the reaction can be efficiently carried out. From the reaction (1-1), 225 ca is removed by HF to 1214 ya. Of 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). Of the reaction, reaction (6-2), 1233zd (Z) is obtained by removing HCl from 243fa, and of reaction (9-2), 1223xd (Z) and / or 1223xd (E) is obtained by removing HCl from 233da The reaction to obtain is mentioned.

Among them, among the reaction (1-1), a reaction to obtain 1214ya from 225ca by deHF, and among the reaction (5-1), a reaction to obtain 1233yd (Z) and / or 1233yd (E) from 244ca by deHF And reaction (9-2) is more preferably a reaction in which 1223xd (Z) and / or 1223xd (E) is obtained from 233da by deHCl.

In the above preferred 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.

In the reaction (1) according to the production method of the present invention, 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).

In the present invention, in the contact, either the compound (A) or the alkaline aqueous solution is in the form of droplets, and the average droplet diameter of the droplets is 1500 μm or less. In the present invention, 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.

Whether the compound (A) is a droplet or an alkaline aqueous solution, the average droplet diameter of the droplet is preferably 800 μm or less, more preferably 600 μm or less, and even more preferably 400 μm or less. The average droplet diameter of the droplets is preferably 1 μm or more, more preferably 5 μm or more, further preferably 10 μm or more, preferably 30 μm or more, and most preferably 50 μm or more. When the average droplet diameter is less than 1 μm, 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 μm 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.

In the production method of the present invention, from the viewpoint of producing a large amount of industrially intended fluorine-containing unsaturated hydrocarbons, 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 | generate by installing a stirring blade in a continuous reactor and stirring it. Examples of 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 (16)
In formula (16), d _i is the inner diameter (m) of the stirring blade, We is the Weber number, and C is a constant.
Here, We = ρ * N ² * d _i ³ / σ.
ρ is the density of the droplet component (kg / m ³ ), N is the rotational speed (rps) of stirring, and σ 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.

In the production method of the present invention, it is necessary to sufficiently stir in order to disperse the droplets of the compound (A) or the alkaline aqueous solution uniformly in the stirring tank. Under such conditions, C is usually 0.052 to 0.17, preferably 0.055 to 0.070.

In the production method of the present invention, 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. For example, 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.

In the production method of the present invention, regardless of the reaction mode, 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 μm or less. Preferably, at any location in the reactor, either the compound (A) or the aqueous alkaline solution is present as droplets, and the average droplet diameter of the droplets is 1500 μm or less.

In addition, in any reaction mode, 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 μm or less. If it is. Preferably, at any time during the reaction, either the compound (A) or the alkaline aqueous solution is present as droplets, and the average droplet diameter of the droplets is 1500 μm 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. From the viewpoint of obtaining sufficient contact with each other, 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). In addition, 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.

When the base is a metal hydroxide, 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.

When the base is a metal oxide, 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. Among them, 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. As the metal oxide, 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.

When the base is a metal carbonate, examples include alkaline earth metal carbonates and alkali metal carbonates. Examples of the alkaline earth metal carbonate include carbonates of metals such as beryllium, magnesium, calcium, strontium, barium, and radium. Examples of the 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). For example, in the reaction of obtaining 1233yd from 244ca by deHF, 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.

For example, in the reaction to obtain 1214ya from 225ca by deHF, 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.

The 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. .

For example, in the reaction for obtaining 1233yd from 244ca by deHF, 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. When the reaction temperature does not reach the above range, the reaction rate and the reaction yield may be reduced. When excessive unreacted 244ca remains, separation from 1233yd may be difficult. Also, when the reaction temperature exceeds the above range, 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.

For example, in the 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.

In addition, in the manufacturing method of this invention, a compound (A) may be used with the by-product and unreacted raw material byproduced at the time of manufacture of a compound (A). For example, 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. Also, for example, in the reaction to obtain 1214ya from 225ca by deHF, 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%. When an isomer mixture is used, the reaction temperature is preferably 0 to 25 ° C. from the viewpoint of suppressing the formation of by-products.

In the production method of the present invention, for the purpose of further promoting the reaction in the reaction system, another substance that does not impair the effects of the present invention may be present. For example, a phase transfer catalyst is preferably present.

Examples of the phase transfer catalyst 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.

Specifically, tetra-n-butylammonium chloride (TBAC), tetra-n-butylammonium bromide (TBAB), methyltri-n-octylammonium chloride (TOMAC) and the like are preferable as the quaternary ammonium salt. Of these, tetra-n-butylammonium chloride (TBAC) and tetra-n-butylammonium bromide (TBAB) are preferable because the reaction can be further promoted, and tetra-n-butylammonium bromide (TBAB) is preferable from the viewpoint of availability. And tetra-n-butylammonium chloride (TBAC) is more preferable from the viewpoint of reactivity.

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.

When the reaction solution contains a phase transfer catalyst, 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.

According to the production method of the present invention, since 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.

According to the production method of the present invention, for example, 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).

In the production method of the present invention, after completion of the reaction, the reaction solution is left to separate into an organic phase and an aqueous phase. In the organic phase, an unreacted compound (A), a by-product and the like may be contained in addition to the target product compound (B). When recovering the compound (B) from the organic phase containing these, it is preferable to employ a separation and purification method such as general distillation.

In addition, 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.

On the other hand, 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. When 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.

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
[Conditions for gas chromatography]
In the production of the following various compounds, the composition analysis of the obtained reaction composition was performed using gas chromatography (GC). DB-1301 (length 60 m × inner diameter 250 μm × thickness 1 μm, manufactured by Agilent Technologies) was used as the column.
[Calculation method of average droplet diameter]
The average droplet diameter was calculated from equation (16). The constant C was 0.060.

[Production Example 1 of 244ca]
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).

<Synthesis of 244ca>
A 2 liter four-necked flask (reactor) equipped with a stirrer, a Dimroth, a condenser, and a glass distillation column (5 stage number measurement) packed with Raschig rings was charged with 1204 g (9.12 mol) of TFPO and N, 12 g (0.17 mol) of N-dimethylformamide (DMF) was added. 1078 g (0.12 mol) of thionyl chloride was added dropwise and stirred at room temperature for 12 hours. Thereafter, the reactor was heated to 100 ° C., and reactive distillation was performed with a reflux timer at a ratio of reflux time / distillation time of 5/1. Distilled 244ca was neutralized with a 20 mass% aqueous potassium hydroxide solution. The recovered 244ca (100% purity) was 979 g (6.50 mol). The required amount of 244ca was produced in the same manner.

[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.

The collected organic layer was washed with water and then analyzed using gas chromatography. 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.
In Examples 1 to 7 and Comparative Example 1, 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. In addition, 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. Thereafter, stirring was continued for 3 hours until the conversion of 244ca reached 99.8% or more, and the organic layer and the aqueous layer were recovered. 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.

[Comparative Example 1]
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.

From the results shown in Table 1, it can be seen that the reaction time decreases as the average droplet diameter decreases. Further, when Examples 1 to 7 and Comparative Example 1 were compared, the reaction time could be effectively shortened by setting the average droplet diameter to 1500 μm or less.

[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. In Examples 8 to 11 and Comparative Example 2, 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. In addition, 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.

[Examples 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.

[Comparative 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.

From the results shown in Table 2, it can be seen that the reaction time decreases as the average droplet diameter decreases. Further, when Examples 8 to 11 and Comparative Example 2 were compared, the reaction time could be effectively shortened by setting the droplet diameter to 1500 μm or less.

It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-082280 filed on April 23, 2018 are cited herein as disclosure of the specification of the present invention. Incorporate.

Claims (11)

1. A fluorine-containing saturated hydrocarbon having a structure of 3 to 7 carbon atoms and having a structure in which one carbon atom of two adjacent 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 with an alkaline aqueous solution to dehydrochlorinate or dehydrofluoride,
   One of the fluorine-containing saturated hydrocarbon and the aqueous alkali solution is brought into contact with droplets having an average droplet diameter of 1500 μm or less.
2. The manufacturing method according to claim 1, wherein the fluorine-containing saturated hydrocarbon has an average droplet diameter of 800 µm or less and is brought into contact with an alkaline aqueous solution.
3. The production method according to claim 1 or 2, wherein the droplets are generated using at least one device selected from a stirring blade, a line mixer, a homogenizer, an ultrasonic generator, and a microbubble generator.
4. The production method according to any one of claims 1 to 3, wherein the droplets are generated by stirring with a stirring blade.
5. The manufacturing method according to any one of claims 1 to 4, wherein an average droplet diameter of the droplets is 1 μm or more and 400 μm or less.
6. The fluorine-containing saturated hydrocarbon is 1-chloro-2,2,3,3-tetrafluoropropane, and the fluorine-containing unsaturated hydrocarbon is 1-chloro-2,3,3-trifluoropropene. Item 6. The production method according to any one of Items 1 to 5.
7. The fluorine-containing saturated hydrocarbon is 1,1-dichloro-2,2,3,3,3-pentafluoropropane, and the fluorine-containing unsaturated hydrocarbon is 1,1-dichloro-2,3,3,3. The production method according to any one of claims 1 to 5, which is tetrafluoropropene.
8. The production method according to any one of claims 1 to 7, wherein the fluorine-containing saturated hydrocarbon is brought into contact with an alkaline aqueous solution in the presence of a phase transfer catalyst.
9. The production method according to claim 8, wherein 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.
10. 10. The production method according to claim 1, wherein the aqueous alkaline solution is an aqueous solution in which at least one base selected from the group consisting of metal hydroxide, metal oxide and metal carbonate is dissolved in water.
11. The production method according to any one of claims 1 to 10, wherein the content of the base in the alkaline aqueous solution is an amount of 0.5 to 48 mass% with respect to the total amount of the alkaline aqueous solution.