WO2019203319A1

WO2019203319A1 - Method for producing fluoroolefin

Info

Publication number: WO2019203319A1
Application number: PCT/JP2019/016682
Authority: WO
Inventors: 英史塩田; 古田　昇二
Original assignee: Ａｇｃ株式会社
Priority date: 2018-04-19
Filing date: 2019-04-18
Publication date: 2019-10-24
Also published as: JP2021120352A

Abstract

Provided is a method for producing, in a liquid phase, a fluoroolefin from hydrofluorocarbon (HFC) or hydrochlorofluorocarbon (HCFC) with high efficiency. A method for producing a fluoroolefin, the method comprising bringing HFC or HCFC, each of which has 3 to 7 carbon atoms and also has, in the molecule thereof, such a structure that a hydrogen atom and a fluorine or chlorine atom are respectively bonded to adjacent two carbon atoms, in a liquid phase into contact with an aqueous alkaline solution in a temperature- and pressure-controllable reaction vessel to cause the removal of a hydrogen halide from the HFC or the HCFC, thereby producing the fluoroolefin, wherein the temperature and the pressure in the reaction vessel are adjusted to values falling within a zone that lies above a water vapor curve of the HFC or the HCFC and also lies below a water vapor curve of the fluoroolefin.

Description

Method for producing fluoroolefin

The present invention relates to a method for efficiently producing a fluoroolefin, specifically, a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin or a chlorofluoroolefin in a liquid phase.

In recent years, hydrofluorocarbons and hydrochlorofluorocarbons 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, halogenated olefins are attracting attention as compounds having a small global warming potential.

As one method for producing halogenated olefins, hydrofluorocarbons or hydrochlorofluorocarbons having a structure in which hydrogen atoms, fluorine atoms or chlorine atoms are bonded to two adjacent carbon atoms in the molecule are dehydrochlorinated. Alternatively, a reaction for dehydrofluorination is 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 hydrofluorocarbon or hydrochlorofluorocarbon 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 is an efficient fluoroolefin in a liquid phase from hydrofluorocarbon or hydrochlorofluorocarbon, specifically, hydrofluoroolefin, perfluoroolefin, hydrochlorofluoroolefin or chlorofluoroolefin. It aims at providing the method of manufacturing.

The present invention achieves the above object and has the following aspects.
[1] A structure in which the number of carbon atoms is 3 to 7 in a reactor capable of adjusting temperature and pressure, and a hydrogen atom and a fluorine atom or a chlorine atom are bonded to two adjacent carbon atoms, respectively. Hydrofluorocarbon (HFC) or hydrochlorofluorocarbon (HCFC) in the molecule is brought into contact with an alkaline aqueous solution in the liquid phase, and the HFC or HCFC is dehydrochlorinated or dehydrofluorinated to produce hydrofluoroolefin (HFO), perfluoro A process for producing a fluoroolefin, which obtains at least one fluoroolefin selected from olefin (PFO), hydrochlorofluoroolefin (HCFO) and chlorofluoroolefin (CFO),
The production method, wherein the temperature and pressure in the reactor are adjusted to be above the vapor pressure curve of the HFC or HCFC and below the vapor pressure curve of the fluoroolefin.

[2] The production method according to [1], wherein the pressure is adjusted by discharging the gas phase in the reactor to the outside of the reactor.
[3] The mass [g] of the compound (A) in the liquid phase in the reactor is L _(A) , the mass [g] of the compound (B) is L _(B), and the compound ( When the mass [g] of _A) is V _(A) and the mass [g] of the compound (B) is V _(B) , the following formula (III) is satisfied, according to [1] or [2] Production method.
(V _(B) / V _(A) ) / (L _(B) / L _(A) ) ≧ 1.5 (III)

[4] Any of [1] to [3], wherein the aqueous alkali 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. 2. The production method according to claim 1.
[5] The production method according to [4], wherein a ratio of the mass of the base to the total mass of the alkaline aqueous solution in the alkaline aqueous solution is 0.5 to 48 mass%.
[6] The production method according to any one of [1] to [5], wherein the hydrofluorocarbon or hydrochlorofluorocarbon is contacted with an alkaline aqueous solution in the presence of a phase transfer catalyst.
[7] The production method according to [6], 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 hydrofluorocarbon or hydrochlorofluorocarbon.
[8] The production method according to [6] or [7], wherein the phase transfer catalyst is a quaternary ammonium salt.
[9] The production according to any one of [6] to [8], wherein the phase transfer catalyst is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide, or methyltri-n-octylammonium chloride. Method.

[10] The production method according to any one of [1] to [9], wherein the hydrofluorocarbon or hydrochlorofluorocarbon is monochlorotetrafluoropropane, and the fluoroolefin is tetrafluoropropene.
[11] The monochlorotetrafluoropropane is 2-chloro-1,1,1,2-tetrafluoropropane and / or 3-chloro-1,1,1,2-tetrafluoropropane, and the tetrafluoropropene is The production method according to [10], which is 2,3,3,3-tetrafluoropropene.
[12] The production method according to [11], wherein the pressure in the reactor is adjusted to 2.0 MPaG or less.
[13] The production method according to any one of [1] to [9], wherein the hydrofluorocarbon or hydrochlorofluorocarbon is dichlorotetrafluoropropane, and the fluoroolefin is monochlorotetrafluoropropene.
[14] The dichlorotetrafluoropropane is 2,3-dichloro-1,1,1,2-tetrafluoropropane and / or 3,3-dichloro-1,1,1,2-tetrafluoropropane, The production method according to [13], wherein the monochlorotetrafluoropropene is 1-chloro-2,3,3,3-tetrafluoropropene.
[15] The production method according to [14], wherein the pressure in the reactor is adjusted to 0.5 MPaG or less.

According to the present invention, a fluoroolefin, specifically, a hydrofluoroolefin, a perfluoroolefin, a hydrochlorofluoroolefin, or a chlorofluoroolefin can be produced efficiently from a hydrofluorocarbon or hydrochlorofluorocarbon in a liquid phase.
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.

It is a graph which shows the vapor pressure curve of 244bb and 1234yf. It is a graph which shows the vapor pressure curve of 234bb and 1224yd (Z) and 1224yd (E). It is the schematic which shows an example of the reaction apparatus used for the manufacturing method of the fluoro olefin of this invention.

The meaning of terms in this specification and the way of description are as follows.
As for “halogenated hydrocarbon”, an abbreviation of the compound is described in parentheses after the compound name, and 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.

“Reaction represented by reaction formula (1)” is referred to as reaction (1). The same applies to reactions represented by other formulas. The “compound represented by the formula (A)” is referred to as the 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.

The “Hansen solubility parameter of a compound (hereinafter also referred to as“ HSP ”)” is composed of a dispersion term, a polar term and a hydrogen bond term. HSP is a literature value or a value estimated by computer software (Hansen Solubility Parameters in Practice (HSPiP) version 4) from the chemical structure of a compound. The HSP of a mixture containing two or more compounds is calculated as a vector sum of values obtained by multiplying the HSP of each compound by the volume ratio of each compound to the entire mixture.
Regarding “pressure”, “MPa” represents “absolute pressure”, and “MPaG” represents “gauge pressure”.

(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 above-mentioned HFC or HCFC which is a starting material (raw material) is represented by the formula (A), and the target product which is HFO, PFO, HCFO or CFO 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.
At least one of Y ¹ , Y ² , R ¹ and R ² is 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 usually carried out in a closed reactor with adjustable temperature and pressure. In the reactor, there exists at least a liquid phase containing the compound (A) and an aqueous alkali solution, and a gas phase. In the liquid phase, the reaction (1) comprises an organic phase mainly composed of the compound (A) and an aqueous alkali solution. It is carried out in the two-phase state of the main water phase. Conventionally, in order to improve the productivity, the two-phase contact is efficiently performed by devising the stirring conditions and equipment, and the reaction is promoted by using a phase transfer catalyst. It has not been easy to increase production efficiency.

In the above production method, the inventor reduced the concentration of the compound (A) in the liquid phase as the reaction (1) progressed in the reactor and the compound (B) was produced from the compound (A). It was confirmed that the reaction rate decreased. Then, by adjusting the temperature and pressure in the reactor so as to be above the vapor pressure curve of the compound (A) and below the vapor pressure curve of the compound (B), the reaction of the reaction (1) It was found that the compound (B) can be produced more efficiently by suppressing the decrease in speed, and the present invention was completed.

In the reaction (1) to which the present invention is applied, the relationship between the molecular weights of the compound (A) and the compound (B) is that the compound (B) is converted into the compound (A) by the amount of HCl or HF removed from the compound (A). ) Smaller molecular weight. Thereby, normally, the compound (B) has a higher vapor pressure and a lower boiling point than the compound (A). Therefore, by adjusting the temperature and pressure in the reactor so as to be above the vapor pressure curve of the compound (A) and below the vapor pressure curve of the compound (B), the compound ( The decrease in the reaction rate is suppressed by suppressing the decrease in the concentration of A).
Hereinafter, in the production method of the present invention, “the temperature and pressure in the reactor are adjusted to be above the vapor pressure curve of the compound (A) and below the vapor pressure curve of the compound (B)” Is referred to as requirement (II).

In the production method of the present invention, by satisfying the requirement (II), the mass [g] of the compound (A) in the liquid phase in the reactor is defined as L _(A), and the mass [g] of the compound (B). Is L _(B) , the mass [g] of the compound (A) in the gas phase is V _(A), and the mass [g] of the compound (B) is V _(B) , the following formula (III) Holds.
(V _(B) / V _(A) ) / (L _(B) / L _(A) )> 1 (III)

In the present invention, when the reaction (1) is carried out under the condition that the formula (III) is established, a decrease in the reaction rate is suppressed. The relationship of formula (III) is preferably maintained from the start to the end of the reaction. The ratio value of (V _(B) / V _(A) ) and (L _(B) / L _(A) ) shown on the left side of the formula (III) is preferably larger, for example, 1.5 or more Is preferable, and 2.0 or more is more preferable. A larger value of the ratio is preferable, and the upper limit is not particularly limited.

In the production method of the present invention, the temperature and pressure in the reactor may vary as long as at least the above requirement (II) is satisfied, but preferably the temperature and pressure are kept constant within the range satisfying the requirement (II). It is preferred that it be retained. Specifically, the pressure in the reactor is preferably adjusted by discharging a predetermined amount of the gas phase outside the reactor. In order to keep the pressure in the reactor constant, it is preferable to continuously discharge the gas phase out of the reactor. Specific temperature and pressure depend on the types of the compound (A) and the compound (B) in the reaction (1) to which the production method of the present invention described below can be applied.

The reaction in the present invention may be performed by a batch method, a semi-continuous method, or a continuous flow method. In the production method of the present invention, when the gas phase is not discharged from the reactor during the reaction, the compound (B) is separated and recovered from the gas phase and liquid phase in the reactor by a usual method after the reaction is completed. When the gas phase of the reactor is discharged from the reactor during the reaction, the compound (B) is separated and recovered from the discharged gas phase, and after completion of the reaction, from the gas phase and liquid phase in the reactor, The compound (B) is separated and recovered by the method.

In the production method of the present invention, when the compound (B) is recovered from the reaction solution (liquid phase) 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 can 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. In some cases, the compound (A) may be recovered from the gas phase, and in this case as well, it can be 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 so as to obtain an appropriate concentration again.

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. If 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 will corrode during its use, and the stability of the compound (B) will decrease. 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.

(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, a production example of fluoropropene shown in the reactions of the following formulas (1-1) to (12-2), (15-1) and (15-2) Is mentioned. As an example in the case of 4 carbon atoms, there can be mentioned a production example of fluorobutene shown in the following reactions of the formulas (13-1) and (13-2). As an example in the case of 5 carbon atoms, there can be mentioned a production example of fluoropentene shown in the following reactions of the formulas (14-1) and (14-2).

Formula (1-1) is a compound represented by 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 deHF. 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 from tetrafluoropropane (HCFC-224eb) by deHCl.

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). ) From HCI-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, the reaction in which the production method of the present invention is suitably used is a reaction in which tetrafluoropropene is obtained from monochlorotetrafluoropropane by deHCl from the viewpoint that the reaction rate can be improved and the reaction can be carried out efficiently. A reaction for obtaining monochlorotetrafluoropropene from dichlorotetrafluoropropane by dehydrochlorination is mentioned.

Examples of the reaction for obtaining tetrafluoropropene from monochlorotetrafluoropropane by removing HCl include 244bb and / or 244eb of formula (7-2) to obtain 1234yf by removing HCl, 244db and / or 244fa of formula (8-2) The reaction to obtain 1234ze (Z) and / or 1234ze (E) by dehydrochlorination from HC1, and the reaction to obtain 1234yf from 244bb and / or 244eb of formula (7-2) by deHCl is more preferred.

Examples of the reaction for obtaining monochlorotetrafluoropropene from dichlorotetrafluoropropane by deHCl to obtain 1224yd (Z) and / or 1224yd (E) from 234bb and / or 234ea of formula (3-2) by deHCl. It is done.

In the above reaction, the effect of the present invention is great particularly when the raw material includes a compound having a CH ₃ group such as 244bb and the elimination of H from the CH ₃ group of the compound is required. Therefore, a high effect can be expected in the reaction of obtaining 1234yf from 244bb by deHCl.

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).

The method for obtaining the compound (A) is not particularly limited. You may manufacture by a well-known method and may use a commercial item. For example, 244bb and / or 244eb in the reaction (7-2) to which the present invention is preferably applied can be produced, for example, by a chlorination reaction in which 254eb is reacted with chlorine. In addition, 234bb and / or 234ea in the reaction (3-2) can be produced, for example, by further chlorinating 244bb and / or 244eb obtained in the chlorination reaction of 254eb.

In the production method of the present invention, the compound (A) may be introduced into the reactor in the form of a mixture containing the compound (A) and impurities. The amount of impurities in the mixture is set so as not to affect the effect of the production method of the present invention. Specifically, the compound (A) may be used together with by-products and unreacted raw materials that are by-produced during the production of the compound (A). For example, the composition of the compound (A) having a purity of 85% by mass or more, preferably 90% by mass or more, particularly preferably 95% by mass or more can be used in the production method of the present invention.

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 composite 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 the 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 1234yf from 244bb and / or 244eb by deHCl, the amount of base relative to 1 mol of 244bb and / or 244eb is from the viewpoint of improving the conversion of 244bb and / or 244eb and the selectivity of 1234yf. 0.2 to 3.0 mol is preferable, and 0.5 to 2.5 mol is more preferable.

Further, for example, in the reaction for obtaining 1224yd (Z) and / or 1224yd (E) from 234bb and / or 234ea by deHCl, the conversion rate of 234bb and / or 234ea and 1224yd (Z) and / or 1224yd (E) From the viewpoint of improving the selectivity, the amount of the base relative to 1 mol of 234bb and / or 234ea is preferably 0.2 to 3.0 mol, and more preferably 0.5 to 2.5 mol.

In the production method of the present invention, preferable temperature and pressure conditions within the conditions satisfying the requirement (II) depend on the types of the compound (A) and the compound (B). In the production method of the present invention, preferable temperature and pressure conditions are described below by taking, as an example, a reaction for obtaining 1234yf from 244bb by deHCl and a reaction for obtaining 1224yd from 234bb by deHCl.

FIG. 1 shows the vapor pressure curves of 244bb and 1234yf. In FIG. 1, the solid line shows a vapor pressure curve of 244bb, and the broken line shows a vapor pressure curve of 1234yf. In each compound, the compound is in a gas phase under temperature and pressure conditions below the vapor pressure curve, and the compound is in a liquid phase under temperature and pressure conditions above the vapor pressure curve. Therefore, in FIG. 1, it can be seen that 44bb is the liquid phase and 1234yf is the gas phase in the temperature and pressure regions surrounded by the vapor pressure curve of 244bb and the vapor pressure curve of 1234yf.

Here, in the reaction to obtain 1234yf from 244bb by deHCl, the reaction temperature is preferably 60 to 120 ° C, and preferably 70 to 115 ° C from the viewpoint of improving the reaction rate and reaction rate and easily suppressing by-products. 70 to 110 ° C. is more preferable. As described above, the pressure in the reactor is set to be equal to or higher than the vapor pressure of 244bb and equal to or lower than the vapor pressure of 1234yf at the reaction temperature. Furthermore, the pressure is preferably 2.0 MPaG or less in terms of the design of the reactor. Therefore, it is preferable to carry out the reaction within a range satisfying these conditions.

FIG. 2 shows vapor pressure curves of 234bb, 1224yd (Z), and 1224yd (E). In FIG. 2, the solid line represents the vapor pressure curve of 234bb, the broken line represents the vapor pressure curve of 1224yd (Z), and the dotted line represents the vapor pressure curve of 1224yd (E). In each compound, the compound is in a gas phase under temperature and pressure conditions below the vapor pressure curve, and the compound is in a liquid phase under temperature and pressure conditions above the vapor pressure curve. Therefore, in FIG. 2, in the temperature and pressure regions surrounded by the vapor pressure curve of 234bb and the vapor pressure curve of 1224yd (E), 234bb is the liquid phase, and 1224yd (Z) and 1224yd (E) are in the gas phase. I know that there is.

Here, in the reaction for obtaining 1224yd from 234bb by deHCl, the reaction temperature and reaction rate are improved, and the reaction temperature is preferably 10 to 90 ° C, more preferably 20 to 80 ° C, from the viewpoint of easily suppressing by-products. preferable. As described above, the pressure in the reactor is set to be equal to or higher than the vapor pressure of 234bb and equal to or lower than the vapor pressure of 1224yd at the reaction temperature. Furthermore, the pressure is preferably 0.5 MPaG or less in terms of the design of the reactor. Therefore, it is preferable to carry out the reaction within a range satisfying these conditions.

1 and FIG. 2, two examples of the reaction of obtaining 1234yf from 244bb by deHCl and the reaction of obtaining 224bb from 234bb by deHCl have been described. However, in the other reactions as well, the compound ( From the vapor pressure curves of A) and compound (B) and preferred reaction temperatures and reaction pressures, preferred temperature and pressure ranges in the production method of the present invention can be set.

In the production method of the present invention, the reaction solution is composed of an organic phase mainly composed of the compound (A) and an aqueous phase composed of an alkaline aqueous solution. 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, it is preferable that a phase transfer catalyst is present. The phase transfer catalyst is present both in the organic phase and in the alkaline aqueous solution, and accelerates the dehalogenation reaction by contact of the compound (A) with the alkaline aqueous solution.

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) or tetra-n-butylammonium bromide (TBAB) is preferable from the viewpoint of further promoting the reaction, and tetra-n-butylammonium bromide (TBAB) (from the point of availability). TBAB) is more preferable, and tetra-n-butylammonium chloride (TBAC) is more preferable from the viewpoint of reactivity.

When a phase transfer catalyst is used in the production method of the present invention, the amount thereof is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the compound (A). More preferably, 0.01 to 3 parts by mass. 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.

In the production method of the present invention, the reaction solution may contain a water-soluble organic solvent capable of dissolving the compound (A) (hereinafter referred to as “water-soluble organic solvent (S)”) together with the phase transfer catalyst. The water-soluble organic solvent (S) is water-soluble and can dissolve the compound (A).

In this specification, the water-solubility in the water-soluble organic solvent (S) means that the water-soluble organic solvent (S) and pure water are mixed at an arbitrary mixing ratio at 25 ° C. without causing phase separation or turbidity. A property that dissolves uniformly. The water-soluble organic solvent (S) can dissolve the compound (A) at 25 ° C. with respect to the compound (A) in such an amount that the water-soluble organic solvent (S) is 20% by mass. When A) and a water-soluble organic solvent (S) are mixed, they are dissolved uniformly without causing phase separation or turbidity.

The water-soluble organic solvent (S) is present both in the organic phase and in the alkaline aqueous solution as in the phase transfer catalyst, and has a function of further enhancing the action of promoting the dehalogenation reaction of the compound (A) in the phase transfer catalyst. Have.

As the water-soluble organic solvent (S), for example, a compound capable of dissolving the compound (A) from a water-soluble alcohol, ketone, ether, ester or the like is appropriately selected and used depending on the type of the compound (A). .

Examples of the water-soluble alcohol include methanol, ethanol, propan-1-ol, butan-1-ol, propan-2-ol, butan-2-ol, 2-methylpropan-2-ol, and 2-methylbutane- Examples of water-soluble ketones such as 2-ol include acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone. Examples of water-soluble ethers include tetraethylene glycol dimethyl ether (hereinafter also referred to as “tetraglyme”), chain ethers such as dimethyl ether, ethyl methyl ether, diethyl ether, and ethylene oxide, and cyclic ethers such as tetrahydrofuran, furan, and crown ethers. Examples of water-soluble esters include methyl acetate and methyl formate.

The water-soluble organic solvent (S) has a property of dissolving the compound (A) in addition to water solubility. The water-soluble organic solvent (S) is a water-soluble organic solvent (S) represented by the following formula (I) based on the Hansen solubility parameter from the viewpoint of further enhancing the action of the phase transfer catalyst in the dehalogenation reaction of the compound (A). ) And the compound (A), the interaction distance (Ra) is preferably 25.0 or less, more preferably 23.0 or less.
_{Ra = [4 × (δD 1} -δD 2) 2 + (δP 1 -δP 2) 2 + (δH 1 -δH 2) 2] 0.5 (I)

Each formula _{(I), δD 1, δP} 1 and delta] H ₁ is the Hansen solubility parameter of the water-soluble organic solvent (S), dispersion term, the polarity term and hydrogen bond, [delta] D _2, [delta] P ₂ and delta] H ₂ is Each represents a dispersion term, a polar term and a hydrogen bonding term in the Hansen solubility parameter of the compound (A), and the unit is (MPa) ^1/2 .

Specifically, for example, when 244bb, 244eb, 234bb, 234ea is used as the compound (A), the interaction distance (Ra) of each compound that is preferable as the water-soluble organic solvent (S) with respect to these compounds (A) ) Is shown in Table 1.

As shown in Table 1, methanol, acetone, tetraglyme, and tetrahydrofuran have an interaction distance (Ra) of 25.0 or less for all of 244bb, 244eb, 234bb, and 234ea. In these dehalogenation reactions, It can be preferably used as the water-soluble organic solvent (S).

In the same manner, a preferred combination of the compound (A) and the water-soluble organic solvent (S) other than those shown in Table 1 can be selected using the interaction distance (Ra) as an index.

The amount of the water-soluble organic solvent (S) used in the production method of the present invention is preferably 1 to 100 parts by weight, more preferably 3 to 80 parts by weight with respect to 100 parts by weight of the compound (A). Part by mass is more preferable. If the amount of the water-soluble organic solvent (S) 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 of use cannot be obtained. It is disadvantageous in terms.

In the production method of the present invention, from the viewpoint of industrially producing a large amount of the desired fluoroolefin, a stirring blade is installed in a batch type, semi-continuous type or continuous type reactor, and it is generated by stirring it. It is preferable. Hereinafter, an example of a reaction apparatus to which the production method of the present invention can be applied will be described with reference to the drawings. FIG. 3 shows a schematic diagram of an example of a reactor used in the method for producing a fluoroolefin of the present invention.

Note that the reaction apparatus shown in FIG. 3 is an exemplification, and the reaction apparatus used in the embodiment of the present invention is not limited to such a structure. If necessary, each member can be deformed, deleted, and changed, and other members can be added.

The reaction apparatus 100 has a configuration in which a reactor body 1, a lid 2, a stirrer 7 having a stirring blade, and a reactor 20 having a thermocouple 8 are installed in a thermostatic bath 5 provided with a heater 6. The reaction apparatus 100 includes a compound (A) storage tank 3 that stores the compound (A) outside the thermostatic chamber 5 and an alkaline aqueous solution storage tank 4 that stores an alkaline aqueous solution. A predetermined amount of the compound (A) and the aqueous alkali solution are supplied into the vessel 20 as a liquid phase leaving a space constituting a gas phase.

The inside of the reactor 20 is composed of a liquid phase L and a gas phase V, and the reaction (1) is performed under the condition that formula (II) is established by adjusting the temperature and pressure in the reactor 20. Under the conditions, the pressure in the reactor 20 increases with the progress of the reaction (1). Therefore, in order to suppress this and keep the pressure in the reactor 20 within a predetermined range, A part of the phase V is recovered in the recovery tank 10 via the discharge line 22.

The reactor 100 has a configuration in which a back pressure valve 9 is provided in the middle of the discharge line 22. By using the back pressure valve 9, the pressure in the reactor 20 is kept constant, and the gas phase V is continuously discharged from the reactor 20. That is, the reaction apparatus 100 is a reaction apparatus that can more effectively implement the production method of the present invention.

In addition, in order to collect the compound (B) easily in the reaction apparatus 100, in order to collect the compound (A) in the gas phase discharged from the reactor 20 between the reactor 20 and the back pressure valve 9. A withstand voltage capacitor or the like may be provided. Thereby, the composition with which content of the compound (B) was raised in the collection tank 10 can be collect | recovered. The vapor phase V recovered in the recovery tank 10 may remove components other than the compound (B) using, for example, molecular sieves.

The material of the constituent members constituting the reaction apparatus 100 includes a compound (A), an aqueous alkaline solution, and a reaction product containing the compound (B), a phase transfer catalyst used arbitrarily, and a water-soluble organic solvent (S). The material is not particularly limited as long as it is inactive to the reaction solution components and the like and is a corrosion-resistant material. For example, glass, iron, nickel, an alloy such as stainless steel mainly containing iron, and the like can be given.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these examples. Examples 1, 2, 5, and 6 are examples, and examples 3, 4, 7, and 8 are comparative 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 (trade name, manufactured by Agilent Technologies, length 60 m × inner diameter 250 μm × thickness 1 μm) was used as the column.

[Example of production of 244bb]
254eb was chlorinated to produce 244bb and 244eb as follows. First, a stainless steel autoclave (internal volume: 6.9 liters) fitted with a quartz tube and a jacket for transmitting light from the light source was cooled to 20 ° C. In this autoclave (hereinafter referred to as a reactor), 2336 g of carbon tetrachloride (CCl ₄ ) and 103 g of 254eb were put, and then visible from an LED lamp (LHT42N-GE39 manufactured by Mitsubishi Electric Corporation, output 40 W). While irradiating light, chlorine gas was introduced into the reactor at a flow rate of 3.2 g / min. As the reaction progressed, heat of reaction was generated and the temperature in the reactor rose to 23.8 ° C. The flow rate chlorine gas was introduced for 2 minutes, that is, 0.10 mol of chlorine was introduced per 1 mol of 254eb, and light irradiation was continued until the temperature in the reactor became constant at 20 ° C. The pressure in the reactor was 0.045 MPa before chlorine supply, and the pressure after chlorine supply, that is, the reaction pressure was 0.045 MPa.

After completion of the reaction, the obtained reaction solution was neutralized by mixing with a 20% by mass aqueous solution of potassium hydrogen carbonate, and then a liquid separation operation was performed. After standing, the reaction composition was recovered from the separated lower layer, and 244bb was obtained by distillation.

[Example 1]
A reactor similar to that shown in FIG. 3 was used. A 0.1 L reactor equipped with a thermocouple and a stirring blade was placed in a constant temperature bath and kept at 80 ° C. In this reactor (autoclave, the same applies below), 588.8 g of 25% by weight NaOH aqueous solution, and 277.0 g of 244bb obtained above (the molar ratio of NaOH to 244bb is NaOH: 244bb = 2: 1). ), 8.3 g of tetra-n-butylammonium bromide (TBAB) as a phase transfer catalyst was added and the reactor was closed.

The stirring blade was rotated at 600 rpm, the back pressure valve was set so that the pressure in the reactor was 0.8 MPaG, and the reaction was performed for 4 hours while discharging the gas phase from the reactor. The gas phase discharged from the reactor was recovered in a recovery tank. After completion of the reaction, the reactor was taken out from the thermostat and cooled to 0 ° C. with ice water to stop the reaction, and the reaction composition was recovered. GC analysis of the reaction composition recovered from the reactor and the gas phase (reaction composition) recovered in the recovery tank was performed to obtain a conversion rate of 244bb and a selectivity of 1234yf. The conversion rate of 244bb was 34.3%, the yield of 1234yf was 34.3%, and the selectivity was 100%.

[Example 2]
In Example 1, the reaction was carried out in the same manner except that the reaction time was changed to 16 hours. As a result, the conversion rate of 244bb was 62.7%, the yield of 1234yf was 62.7%, and the selectivity was 100%.

[Example 3]
In Example 1, a 244bb deHCl reaction for 4 hours was performed in the same manner except that the gas phase was not discharged from the reactor. When the pressure in the reactor during the reaction was specified, it was 2.1 MPaG, which was in the upper region of the vapor pressure curve of 1234yf in FIG. After completion of the reaction, the recovered reaction composition was subjected to GC analysis to obtain a conversion rate of 244bb and a selectivity of 1234yf. The conversion of 244bb was 29.1%, the yield of 1234yf was 29.1%, and the selectivity was 100%.

[Example 4]
In Example 3, the reaction was carried out in the same manner except that the reaction time was changed to 16 hours. As a result, the conversion rate of 244bb was 51.3%, the yield of 1234yf was 51.3%, and the selectivity was 100%.

[Production example of 234bb]
1234yf was chlorinated as follows to produce 234bb.
First, a stainless steel reactor (internal volume 2.3 liters) equipped with a quartz tube and a jacket that transmits light from the light source was cooled to 0 ° C. In this reactor, 1395 g of carbon tetrachloride (CCl ₄ ) was added as a solvent, and then 1234yf was flowed at a flow rate of 245 g per hour while irradiating visible light from a fluorescent lamp (Neocompact EFP12EL manufactured by Toshiba Corporation, output 12 W). Then, chlorine gas was supplied into the reactor at a flow rate of 152 g per hour.

As the reaction progressed, reaction heat was generated, the temperature in the reactor rose to 7.6 ° C., and the pressure in the reactor rose to 0.08 MPaG. The reaction was continued for 1 hour while supplying 1234yf and chlorine gas at the above flow rates. After confirming that 245g of 1234yf and 152g of chlorine were supplied, the supply of 1234yf and chlorine was stopped, and the pressure in the reactor was Light irradiation was continued until normal pressure was reached. After completion of the reaction, the obtained reaction solution was neutralized with a 20% by mass aqueous potassium hydrogen carbonate solution, and then a liquid separation operation was performed. After standing, 1734 g of product (1) was recovered from the separated lower layer. The product (1) was distilled by a normal operation to obtain 234bb with a purity of 99.8%.
After completion of the reaction, the obtained reaction solution was neutralized by mixing with a 20% by mass aqueous solution of potassium hydrogen carbonate, and then a liquid separation operation was performed. After standing, the reaction composition was recovered from the separated lower layer, and 234bb was obtained by distillation.

[Example 5]
A reactor similar to that shown in FIG. 3 was used. A 0.1 L reactor equipped with a thermocouple and a stirring blade was placed in a constant temperature bath and kept at 30 ° C. In this reactor, 478.5 g of a 20% by mass NaOH aqueous solution, and 276.6 g of 234bb obtained above (the molar ratio of NaOH and 234bb is NaOH: 234bb = 2: 1) as a phase transfer catalyst. Of tetra-n-butylammonium bromide (TBAB) was added and the reactor was closed.

The stirring blade was rotated at 600 rpm, the back pressure valve was set so that the pressure in the reactor became 0 MPaG, and the reaction was carried out for 1 hour while discharging the gas phase from the reactor. The gas phase discharged from the reactor was recovered in a recovery tank. After completion of the reaction, the reactor was taken out from the thermostat and cooled to 0 ° C. with ice water to stop the reaction, and the reaction composition was recovered. GC analysis of the reaction composition recovered from the reactor and the gas phase (reaction composition) recovered in the recovery tank was performed to obtain a conversion rate of 234bb and a selectivity of 1224yd. The conversion of 234bb was 54.1%, the yield of 1224yd was 54.1%, and the selectivity was 100%.

The obtained 1224yd was a mixture of 1224yd (Z) and 1224yd (E). As shown in FIG. 2, in this example, the reaction was performed in a region higher than the vapor pressure curve of 234bb and lower than the vapor pressure curves of 1224yd (Z) and 1224yd (E). The conversion rate of 1224yd shown above is the sum of the conversion rates of 1224yd (Z) and 1224yd (E).

[Example 6]
In Example 5, the reaction was carried out in the same manner except that the reaction time was changed to 2 hours. As a result, the conversion rate of 234bb was 63.4%, the yield of 1224yd was 63.4%, and the selectivity was 100%.

[Example 7]
In Example 5, a 234bb deHCl reaction for 1 hour was performed in the same manner except that the gas phase was not discharged from the reactor. When the pressure in the reactor during the reaction was specified, it was 0.15 MPaG and was in the upper region of the vapor pressure curve of 1224yd (Z) in FIG. After completion of the reaction, the recovered reaction composition was subjected to GC analysis to determine a conversion rate of 234bb and a selectivity of 1224yd. The conversion rate of 234bb was 50.5%, the yield of 1224yd was 50.5%, and the selectivity was 100%.

[Example 8]
In Example 7, the reaction was carried out in the same manner except that the reaction time was changed to 2 hours. As a result, the conversion rate of 234bb was 58.2%, the yield of 1224yd was 58.2%, and the selectivity was 100%.

It should be noted that the entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-080600 filed on April 19, 2018 are cited herein as disclosure of the specification of the present invention. Incorporate.

Claims

In a reactor with adjustable temperature and pressure, the number of carbon atoms is 3 to 7, and a structure in which a hydrogen atom and a fluorine atom or a chlorine atom are bonded to two adjacent carbon atoms, respectively, in the molecule The hydrofluorocarbon or hydrochlorofluorocarbon is brought into contact with an alkaline aqueous solution in a liquid phase, and the hydrofluorocarbon or hydrochlorofluorocarbon is dehydrochlorinated or dehydrofluorinated to produce hydrofluoroolefin, perfluoroolefin, hydrochlorofluoroolefin and chlorofluoro A process for producing a fluoroolefin, which obtains at least one fluoroolefin selected from olefins, comprising:
A production method in which the temperature and pressure in the reactor are adjusted to be above the vapor pressure curve of the hydrofluorocarbon or hydrochlorofluorocarbon and below the vapor pressure curve of the fluoroolefin.
The production method according to claim 1, wherein the pressure is adjusted by discharging the gas phase in the reactor to the outside of the reactor.
The mass [g] of the compound (A) in the liquid phase in the reactor is L (A) , the mass [g] of the compound (B) is L (B), and the compound (A) in the gas phase The manufacturing method of Claim 1 or 2 which satisfy | fills following formula (III), when mass [g] is set to V (A) and mass [g] of a compound (B) is set to V (B) .
(V (B) / V (A) ) / (L (B) / L (A) ) ≧ 1.5 (III)
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.
The production method according to claim 4, wherein the ratio of the mass of the base to the total mass of the alkaline aqueous solution in the alkaline aqueous solution is 0.5 to 48 mass%.
The production method according to any one of claims 1 to 5, wherein the hydrofluorocarbon or hydrochlorofluorocarbon is contacted with an alkaline aqueous solution in the presence of a phase transfer catalyst.
The production method according to claim 6, 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 hydrofluorocarbon or hydrochlorofluorocarbon.
The production method according to claim 6 or 7, wherein the phase transfer catalyst is a quaternary ammonium salt.
The production method according to any one of claims 6 to 8, wherein the phase transfer catalyst is tetra-n-butylammonium chloride, tetra-n-butylammonium bromide or methyltri-n-octylammonium chloride.
The production method according to any one of claims 1 to 9, wherein the hydrofluorocarbon or hydrochlorofluorocarbon is monochlorotetrafluoropropane, and the fluoroolefin is tetrafluoropropene.
The monochlorotetrafluoropropane is 2-chloro-1,1,1,2-tetrafluoropropane and / or 3-chloro-1,1,1,2-tetrafluoropropane, and the tetrafluoropropene is 2,3 The production method according to claim 10, which is 1,3,3-tetrafluoropropene.
The production method according to claim 11, wherein the pressure in the reactor is adjusted to 2.0 MPaG or less.
The production method according to any one of claims 1 to 9, wherein the hydrofluorocarbon or hydrochlorofluorocarbon is dichlorotetrafluoropropane, and the fluoroolefin is monochlorotetrafluoropropene.
The dichlorotetrafluoropropane is 2,3-dichloro-1,1,1,2-tetrafluoropropane and / or 3,3-dichloro-1,1,1,2-tetrafluoropropane, and the monochlorotetrafluoropropane is The production method according to claim 13, wherein the propene is 1-chloro-2,3,3,3-tetrafluoropropene.
The production method according to claim 14, wherein the pressure in the reactor is adjusted to 0.5 MPaG or less.